Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

Abstract

This review surveys recent progress in the chemistry of polycyclic heteroaromatic molecules with a focus on structural diversity and synthetic methodology. The article covers literature published during the period of 2016-2020, providing an update to our first review of this topic (Chem. Rev. 2017, 117 (4), 3479-3716).

Figure 1

Partial citation timeline of CR2017 and the new references included in the present Review.

Chart 1. Examples of PHA-Based Materials

Scheme 1. Carbocycle Formation via Cyclization and Annulation Reactions

π-Conjugation is implicit in shaded rings. Numbers correspond to representative schemes and charts.

Scheme 2. Heterocycle Formation via Cyclization Reactions

π-Conjugation is implicit in shaded rings. Numbers correspond to representative schemes and charts.

Scheme 3. Heterocycle Formation via Annulation Reactions

π-Conjugation is implicit in shaded rings. Numbers correspond to representative schemes and charts.

Scheme 4. Synthesis of a HBC-Like System Containing a Pyrrole Ring

Reagents and conditions: (a) 2,3,4,5-tetrakis(4-tert-butylphenyl)cyclopenta-2,4-dien-1-one, toluene, 200 °C, 18 h for 4.1a 72 h for 4.1b; (b) 2,3,4,5-tetrakis(4-(t-butyl)phenyl)cyclopenta-2,4-dien-1-one, THF, dioxane, Co₂(CO)₈, 160 °C, 15 min, microwave, 350 W; (c) FeCl₃, DCM, MeNO₂, 0 °C.

Scheme 5. Synthesis of π-Extended Pyridines

Reagents and conditions: (a) Cs₂CO₃ (2 equiv), 10 mol % of Pd(PPh₃)₄, THF/H₂O (4:1), 17–24 h, 80 °C, N₂; (b) 5.4a: DDQ (7 equiv), TfOH (14 equiv), DCM, 1 h, 0 °C, N₂; 5.4b: DDQ (7 equiv), TfOH (14 equiv), DCM, 4 h, −50 °C to −20 °C, N₂; (c) (1) MeI (excess), CH₃CN, 2 h, rt, N₂, (2) Ag(OTf) (2.1 equiv), 15 min, rt, N₂; (d) m-CPBA (1 equiv), CHCl₃, 24 h, 0 °C to rt; (e) tetrakis(4-tert-butylphenyl)porphyrinato zinc (1 equiv), C₆D₆, rt.

Scheme 6. Synthetic Routes to Diazacoronene Diimides and Tetraesters

Reagents and conditions: (a) picolinaldehyde, dry DMF, TFA, molecular sieves 3 Å, 110 °C, N₂ to O₂, 21 h; (b) picolinaldehyde, dry DMF, TFA, molecular sieves 3 Å, 110 °C, N₂ to O₂, 18 h; (c) (1) H₂SO₄, AcOH, reflux, 17 h, (2) RNH₂, imidazole, pyridine, 120 °C, 6 h.

Scheme 7. Synthetic Route to Bis(amide)-Containing Coronene

Reagents and conditions: (a) (1) NaNO₂, H₂SO₄, (2) KI, water, (3) hex-1-yn-1-yl copper, pyridine; (b) urea, DMF; (c) [Rh^IIICp·(MeCN)₃](SbF₆)₂, TFE, 120 °C, 14 h, (2) DMAP, TFE, 140 °C, 14 h.

Scheme 8. Pyrimidine-Containing Nanographenes

Reagents and conditions: (a) Br₂, toluene, 90 °C, 2 h; (b) Br₂, rt, 25 min; (c) Br₂, CHCl₃, reflux, 3 h.

Scheme 9. Synthesis of π-Extended Biscoumarins

Reagents and conditions: (a) K₂CO₃, DMSO, 100 °C; (b) hν, THF, rt; (c) K₂CO₃, DMSO, 100 °C; (d) BBr₃, DCM, −40 °C to rt; (e) C₆H₁₃Br, K₂CO₃, DMF, 60 °C; (f) FeCl₃, DCM, rt.

Scheme 10. 1,5,9-Triazacoronene Derivatives

Reagents and conditions: (a)⁻ various aldehydes, DMSO, 130–150 °C, in Ar, then in air; (b) (1) DMF or NMP, TfOH, 120 °C, 12 h, (2) 6 equiv of K₂CO₃, 120 °C, 12 h; (c) DMF/dioxane (10:1 v/v), AcOH, TfOH.

Scheme 11. From Anthraquinone to a Heteracoronene

Reagents and conditions: (a) Pd₂(dba)₃, BINAP, Cs₂CO₃, toluene, 105 °C, 24 h; (b) CH₃CO₂K, DMF, microwave, 170 °C, 30 min.

Scheme 12. Synthesis of Pyrimidine-Containing Hexaaza-HBCs

Reagents and conditions: (a) Co₂(CO)₈, dioxane, 115 °C, 24 h, under N₂; (b) FeCl₃, CH₃NO₂, 298 K, Ar bubbling, 72 h; (c) DDQ, MeSO₃H or CF₃SO₃H, DCM.

Scheme 13. Synthesis and Structures of Peripherally Fused Azacoronenes and Their Analogues

Reagents and conditions: (a) NOSbF₆ (2.0 equiv) and DCM, rt, 10 min; (b) 3,4-dihexylpyrrole, NaH, DMF, rt; (c) FeCl₃, CH₃NO₂, rt; (d) I₂ (excess), reflux, under N₂ flow; (e) AgNO₂ (9.7 equiv), DCM, rt; (f) DMF or N,N-dimethylbenzamide, POCl₃, KPF₆, DCE; (g) NOSbF₆ or BAHA, DCM.

Chart 2. Radially π-Extended Pyrrole-Fused Azacoronenes

Scheme 14. Synthesis of an Azacoronene Nanosandwich

Reagents and conditions: (a) 6 equiv of 10-camphorsulfonic acid, 4 equiv of paraformaldehyde, CHCl₃, pressure tube, 90 °C, 17 h; (b) toluene, 365 nm irradiation, air.

Scheme 15. Synthesis of Diaza-HBP and Internally N-Doped Diaza-HBC

Reagents and conditions: (a) (1) tributylamine, DMSO, 190 °C, Ar, (2) DDQ, C₂D₂Cl₄, 100 °C; (b) in vacuo on the Ag(111) surface, 270 °C.

Scheme 16. Synthesis of OBO-Doped peri-Tetracenes via Bistetracenes

Reagents and conditions: (a) BBr₃, o-DCB, rt to 150 °C, 12 h; (b) DDQ, TfOH, DCM, 0 °C to rt.

Scheme 17. Bottom-Up Synthesis of Substitutionally Boron-Doped Graphene Nanoribbons

Reagents and conditions: (a)^, Au(111), 200–220 °C; (b) Au(111), 300–400 °C.

Scheme 18. Coronenoid Containing Four NBN Units

Reagents and conditions: (a) CBr₄, PPh₃, DCM, −50 to 25 °C; (b) R-NH₂, t-BuONa, Pd₂(dba)₃, dppf, toluene, 120 °C; (c) BF₃·Et₂O, Et₃N, DCM, 50 °C.

Scheme 19. Synthesis of a BN-Doped Hexa-peri-hexabenzocoronene

Reagents and conditions: (a) BCl₃, toluene, reflux; (b) THF, −84 °C to rt; (c) [i-Pr₃Si][CB₁₁H₆Cl₆], Me₂SiMes₂, PhCl, 110 °C, Schlenk line.

Scheme 20. One-Shot Multiple Borylation toward BN-Doped Nanographenes

Reagents and conditions: (a) BI₃, Ph₃B, o-DCB, reflux, 20 h; (b) BI₃, Ph₃B, 1,2,4-trichlorobenzene, 200 °C, 20 h; (c) BI₃, o-DCB, reflux, 12 h.

Scheme 21. Propeller-Shaped Nanographene

Reagents and conditions: (a) Co₂(CO)₈, dioxane, 120 °C; (b) hν, CHCl₃.

Scheme 22. Synthesis of Oxa[7]superhelicene

Reagents and conditions: (a) 2,3,4,5-tetrakis(4-tert-butylphenyl)cyclopenta-2,4-dien-1-one (2.5 equiv), toluene, N₂, 23 h, 220 °C (pressure flask); (b) anhydrous FeCl₃ (35 equiv), MeNO₂, DCM, N₂, 25 min at 0 °C, 20 h at rt; (c) DDQ (15 equiv), triflic acid (30 equiv), DCM, N₂, 25 min at 0 °C, 20 h at rt.

Scheme 23. Persulfurated Coronene

Reagents and conditions: (a) phenylmethanethiol, NaH, DMI, 0 °C to rt, 16 h; (b) (1) Li, THF, MeOH, NH₃, −78 °C to rt, 4 h, (2) HCl/H₂O₂/water, rt; (c) NaBH₄.

Chart 3. Peripherally Fused HBC Systems^,

Scheme 24. Coronene-Containing N-Heteroarenes

Reagents and conditions: (a) I₂, hν, rt; (b) Pd(dba)₂, RuPhos, DIPEA, CHCl₃, 60 °C; (c) MnO₂, CHCl₃, rt.

Scheme 25. cata-Condensed Heteroannulated Coronenes

Reagents and conditions: (a) 2.2 equiv of NBS, DCM, rt, 1 h; (b) 5 mol % of Pd₂(dba)₃, 7.5 mol % of t-Bu₃P·HBF₄, THF, K₂CO₃, 80 °C 16 h; (c) I₂, hν, propylene oxide, cyclohexane, 4 h.

Scheme 26. Synthesis of O- and S-Doped Contorted Coronenes

Reagents and conditions: (a) Pd(OAc)₂, SPhos, K₃PO₄, dioxane/water, 60 °C; (b) hν, I₂, toluene, 2-methyloxirane.

Scheme 27. Sulfur-Doped Three-Dimensional Nanographenes

Reagents and conditions: (a) 2,3,4,5-tetrakis(4-tert-butylphenyl)cyclopenta-2,4-dien-1-one, MW, 300 °C; (b) FeCl₃, MeNO₂, DCM, 0 °C.

Scheme 28. Tris(benzothiophene)-Fused Hexa-peri-hexabenzocoronenes

Reagents and conditions: (a) FeCl₃, DCM, MeNO₂, rt, 1 h; (b) m-CPBA, THF, rt, 1 h.

Chart 4. Ryleneimide–HBC Hybrids

Scheme 29. Synthesis of N-Doped Benzo[ghi]perylene and Its Dication

Reagents and conditions: (a) I₂, propylene oxide, hν (500 W high-pressure mercury vapor lamp), rt, 2 h, 64%; (b) (1) CH₃I, MeCN, reflux, overnight, (2) KPF₆, acetone, 2 h, 95%; (c) MeOH, hν (500 W high-pressure mercury vapor lamp), O₂, 10%; (d)^, iodine, propylene oxide, toluene, hν.

Scheme 30. Synthesis of Azaperylenes Through Intramolecular C–H Activation

Reagents and conditions: (a) [Pd₂(dba)₃]·CHCl₃, P(m-tolyl)₃, Cs₂CO₃, 1-chloronaphthalene, 160 °C, 16 h, 50%; (b) Pd(PPh₃)₂Cl₂, Cs₂CO₃, mesitylene, 120 °C, 16 h, 25%.

Scheme 31. Synthesis of Extended Perylenoids Containing a Coumarin Substructure

Reagents and conditions: (a) 1-naphthylboronic acid, Pd(PPh₃)₄, K₂CO₃, 4:1 toluene/H₂O, 90 °C, 2 h, 87%; (b) AlCl₃, NaCl, 140 °C, 4 h, 38%; (c) NBS, Bz₂O₂, DCM, 30 °C, 12 h, 89%; (d) RB(OH)₂, Pd(PPh₃)₂Cl₂, K₃PO₄, 5:1 EtOH/H₂O, 90 °C, 8 h, then 5:1 EtOH/H₂O, air, hν (blue LED), rt, 3 h, 54–87%; (e) MeSO₃H, rt, 16 h, 58%; (f) MeI, K₂CO₃, DMF, rt, 5 h, 85% or 1-bromopentane, Na₂CO₃, KI, DMF, reflux, 16 h, 48%; (g) NBS, Bz₂O₂, CHCl₃, rt, 1 h, 82–84%.

Scheme 32. Synthesis of π-Extended Triangulenium Dyes

Reagents and conditions: (a) (1) Al, H₂SO₄, 25 °C, 18 h, (2) glycerol, H₂SO₄, 125 °C, 3.5 h; (b) m-dimethoxybenzene, TMEDA, n-BuLi, 1:1 benzene/Et₂O, rt, 1 h; (c) (1) 48% HBr_(aq), AcOH, reflux, 48 h, (2) 0.2 M KPF_6(aq); (d) neat, 225 °C, 5 h; (e) Li, o-bromoanisole, benzene/Et₂O, reflux, 30 min; (f) pyridine hydrochloride, 190 °C, 5 min; (g) methylamine, PhCO₂H, NMP, 90–95 °C, 18 h; (h) PPA, 110 °C, 30 h; (i) (1) m-dimethoxybenzene, TMEDA, n-BuLi, 1:1 benzene/Et₂O, reflux, 2 days, (2) 6 M HCl_(aq), 0.2 M KPF_6(aq); (j) PPA, 110 °C, 1 h.

Scheme 33. Indole-Fused Boraperylene Prepared by Electrophilic Borylation

Reagents and conditions: (a) BCl₃, 2,4,6-tri(tert-butyl)pyridine, AlCl₃, DCM, 1 h; (b) 2,4,6-tri(tert-butyl)pyridine, 2,6-dichloropyridine, AlCl₃, DCM, rt, 18 h.

Scheme 34. Synthesis of Boron-Doped Perylene

Reagents and conditions: (a)^, (1) HNTf₂, chlorobenzene, rt, 90 min then 34.1a added, 110 °C, 5 h or 34.1b added, 160 °C, 24 h, (2) TEMPO, 80 °C, 36 h for 34.1a or 24 h for 34.1b, (3) hydrolytic workup (b) (1) BBr₃, DCM, rt, 24 h, (2) MesMgBr, toluene, rt.

Scheme 35. Synthesis of a Boron-Doped Tetrabenzopentacene

Reagents and conditions: (a) 1,8-dibromonaphthalene, 1 equiv of n-BuLi, Et₂O, 0 °C – rt, 45 min, then 35.1, rt, overnight, 86%; (b) Ni(cod)₂, cod, 2,2′-bipyridyl, pyridine, rt, 24 h, 79%; (c) Ni(cod)₂, cod, 2,2′-bipyridyl, THF, rt, 24 h, 81%.

Scheme 36. Synthesis of a Coil-Shaped Dioxaperylenoid Polymer

Reagents and conditions: (a) K₂CO₃, diphenyl sulfone, 210 °C, 5 h; (b) (1) H₂SO₄, 160 °C, 6 h, (2) tetrabutylammonium iodide, 120 °C, 6 h.

Scheme 37. Photocyclization of Monomethylated Diazaxanthilidene

Reagents and conditions: (a) H₂O, hν (fluorescent light bulb), 3 days, 64%.

Scheme 38. Synthesis of a Sulfur-Doped Perylenoid

Reagents and conditions: (a) I₂, CHCl₃, 1 h at 70 °C, 1 h at 80 °C, 22 h at 90 °C.

Scheme 39. Synthesis of a Diazonia Derivative of Hexabenzoperylene

Reagents and conditions: (a)p-phenylenediamine, DMF, 150 °C, 20 h, 39%; (b) 2:5 MeOH/DCM, air, hν (450 W high-pressure mercury vapor lamp), 14 h, 15%.

Scheme 40. Synthesis of N-Doped Tetrabenzopentacenes and N-Doped Rubicenes

Reagents and conditions: (a) KOH, o-xylene, reflux; (b) Pd(OAc)₂, PCy₃, DBU, DMA, 150 °C; (c) KOH, quinoline, 180 °C.

Scheme 41. Synthesis of 7,8-Diazabenzo[ghi]peryleneimide and 1,2-Diazonia-7,8-diazabenzo[ghi]peryleneimide

Reagents and conditions: (a) (1) maleic anhydride, p-chloranil, 220 °C, (2) 4-heptylamine, 150 °C; (b) p-chloranil, 150 °C.

Scheme 42. Synthesis of Diazaperylenoids via Metal-Free C(sp³)–H Aminations with Unprotected Anilines

Reagents and conditions: (a)t-BuOK, O₂, DMF, 120 °C.

Scheme 43. Synthesis of 1,7-Diazaperylene and Its Dialkyl Derivatives

Reagents and conditions: (a) NOHSO₄, conc. H₂SO₄, rt, 1 h, 91%; (b) CuCl, H₂SO₄, t-BuOH, 55–60 °C, then 10:1 25% NH₃(aq)/CHCl₃, rt, 24 h, 25%.

Scheme 44. Synthesis of 1,7-Diazaperylene Diimides

Reagents and conditions: (a) methyl cyanoacetate, KOt-Bu, DMSO, 50 °C, 3 h, 38%; (b) H₂SO₄, rt, 30 min, 87%; (c) Tf₂NPh, DMAP, Et₃N, DCM, −20 °C to rt, 2 h, 22%; (d) Pd(PPh₃)₄, HCOOH, Et₃N, DMF, 80 °C, 2 h, 83%; (e) NBS, H₂SO₄, 50 °C, 2.5 h, 47%; (f) 2,4,6-trichlorophenyl formate, Pd(OAc)₂, Xantphos, Et₃N, toluene, 100 °C, 12 h, 22%; (g) TsOH·H₂O, o-dichlorobenzene, 120 °C, 24 h, 89%; (h) RNH₂, EtCOOH, o-dichlorobenzene, 150 °C, 11–38 h.

Scheme 45. Synthesis of N,S- and N,O-Containing Benzoperylene Derivatives

Reagents and conditions: (a)t-BuONa, Pd(OAc)₂, Pd₂(dba)₃, Cy₃P, (t-Bu)₃P, toluene, 90 °C, 10 h.

Scheme 46. π-Extended Dioxaperylenoid

Reagents and conditions: (a) BBr₃, DCM, 0 °C to rt, overnight; (b) CuO, nitrobenzene, air, 200 °C, overnight.

Scheme 47. Synthesis of Bridged Tetraaryl-p-quinodimethanes

Reagents and conditions: (a) conc. H₂SO₄, 140 °C, 3 h; (b) conc. H₂SO₄, 75 to 100 °C, 48 h, then 160 °C, 2 h (6 h for 47.5a); (c) conc. H₂SO₄, 95 to 130 (150) °C, 78 (75) h (47.5e); (d) AgSbF₆, DCM, rt; (e) DDQ, DCM, rt.

Scheme 48. Synthesis of Azaterrylene Derivatives

Reagents and conditions: (a) (1) Sc(OTf)₃, DDQ, xylene, 165 °C, 1 day, (2) N₂H₂·H₂O, rt, 1 h; (b) (1) potassium, xylene, 130 °C, 16–17 h, (2) air, 4 h.

Scheme 49. Synthesis of Azaperylenes via Radical Anion Coupling

Reagents and conditions: (a) (1) 10–12 equiv of K, DME, rt, or DME, 100 °C for 49.2f, or toluene, 95 °C for 49.2e, ca. 1 day, (2) air, 4 h.

Scheme 50. Synthesis of O-Doped Benzorylenes

Reagents and conditions: (a) CuI, pivalic acid, DMSO, 130–145 °C; (b) BBr₃, DCM, 0 °C.

Scheme 51. Synthesis of BO- and BNO-Doped Perylenoids

Reagents and conditions: (a) (1) t-BuLi, chlorobenzene, −45 °C, 4 h or −45 to 0 °C, 3 h, (2) BBr₃, (3) 40 °C, 24 h; (b) (1) BBr₃, o-dichlorobenzene, 150 °C, 12 h; (c) BBr₃, o-dichlorobenzene, 180 °C, 24 h; (d) 6 equiv of BI₃, 1,2,4-trichlorobenzene, 180 °C, 20 h.

Scheme 52. Synthesis of BN- and BO-Doped Perylenoids

Reagents and conditions: (a) LiAlH₄, Et₂O, 0 °C to rt, 12 h, then Me₃SiCl, −78 °C to rt, 12 h; (b) C₆H₆, 50 °C, 4.5 h; (c) Mg, THF, 50 °C, 2.5 h; (d) R–CC–SnR′₃, Pd(Pt-Bu₃)₂, toluene, 80 °C, 4 h, then rt, 14 h; (e) 10–20 mol % of (Ph₃P)Au(NTf₂), DCM, 60 °C, 4 h; (f) TMS₂NMe, C₆D₆, 120 °C, 2 days; (g) 25 mol % of (Ph₃P)Au(NTf₂), DCM, 60 °C, 2 days.

Scheme 53. Formation of Tetraazaperylenoids on the Gold Surface

Reagents and conditions: (a) Thermal deposition on the Au(111) surface in a vacuum and then annealing at 470–550 K.

Scheme 54. Synthesis of Phenothiazine Dimers

Reagents and conditions: (a) DDQ, CHCl₃, rt, 7 h; (b) DDQ, Sc(OTf)₃, CHCl₃, reflux, 23 h; (c) (1) DDQ, DCM, rt, 2 h, (2) DDQ, Sc(OTf)₃, reflux, 18 h; (d) Ni(cod)₂, cod, 2,2′-bipyridyl, THF, 60 °C, 24 h; (e) DDQ 3.1 equiv, CHCl₃, rt, 24 h, then N₂H₄·H₂O; (f) m-CPBA, CHCl₃, rt, 40 min.

Scheme 55. Synthesis of Phenothiazine-Containing Buckybowls

Reagents and conditions: (a) CuI, K₂CO₃, 18-crown-6, o-dichlorobenzene, 180 °C, 48 h; Pd(OAc)₂, PCy₃·HBF₄, K₂CO₃, DMA, 170 °C, 48 h; (c) 30% H₂O₂, AcOH, CHCl₃, 60 °C, 12 h; (d) AgSbF₆ (1 or 2 equiv), dry DCM, rt, 20 min.

Scheme 56. Synthesis of Heteroatom-Annulated Perylene Tetraesters

Reagents and conditions: (a) KOH, H₂O, 70 °C, 0.5 h, then acidified to pH 8–9 with 1 M HCl, then Aliquat 336, KI, RBr, reflux, 12 h, 69–75%; (b) NaNO₂, HNO₃, DCM, 0 °C, 1 h, 80–90%; (c)^,, P(OEt)₃, reflux, 4 h, 55–62%; (d)^, sulfur powder, NMP, 70 °C, 0.5 h, then 180 °C, 17 h, 50–60%; (e)^, selenium powder, NMP, 70 °C, 0.5 h, then 180 °C, 17 h, 52–58%; (f) NaH, RBr, THF, reflux, 17 h, 70–80%.

Scheme 57. Synthesis of N-Annulated Perylene Monoimides and Diimides

Reagents and conditions: (a) p-toluenesulfonic acid monohydrate, toluene, 100 °C, 30 h, 90%; (b) tris(n-dodecyloxy)benzylamine (2.05 equiv), zinc acetate, imidazole, 165 °C, microwave, 30 min, 80–90%; (c) n-octadecylamine (1.1 equiv), imidazole, 165 °C, microwave, 35 min, 55%.

Scheme 58. Synthesis of Unsubstituted N- and S-Annulated Perylenes

Reagents and conditions: (a) sulfur powder, NMP, 70 °C, then 58.1, 180 °C, 10 h, 50%; (b) P(OEt)₃, reflux, 2 h, 85%; (c) m-CPBA, DCM, −78 to 5 °C, 19%; (d) NBS, 1:1 CHCl₃/AcOH, rt, 5 h; (e) α,α′-dibromo-p-xylene, KOH, KI, THF, reflux, 2 days, 50%; (f) N-methyl-4,4′-bipyridinium hexafluorophosphate, MeCN, reflux, 12 h, 50%.

Scheme 59. Preparation of a NAP Diimide Dimer via Suzuki–Miyaura Coupling Using Nitro and Bromo Derivatives

Reagents and conditions: (a) NaN₃, 1:1 DMF/THF, rt, 18 h, 76%; (b) 1-bromooctane, K₂CO₃, KI, DMF, 90 °C, 18 h, 85%; (c) Br₂, DCM, rt, 30 min, quant.; (d) HNO₃ (fuming), DCM, rt, 5 min, 66%; (e) 1,4-benzenediboronic acid bis(pinacol) ester, Pd(PPh₃)₄, K₂CO₃, 9:1 dioxane/H₂O, 110 °C, microwave heating, 2 h.

Scheme 60. O-, S-, and Se-Annulation of Perylene Diimides

Reagents and conditions: (a)^, NMP, O₂, 180 °C, 5 h, 30%; (b) sulfur powder, NMP, 130 °C, 12 h, 32%; (c) sulfur powder, NMP, 70 °C then 60.1b, 190 °C, 3 h, 52%; (d) selenium powder, NMP, 70 °C then 60.1b, 190 °C, 3 h, 48%.

Scheme 61. Synthesis of S- and S₂-Annulated Perylene Diimides

Reagents and conditions: (a) HNO₃, CAN, DCM, 25 °C, 2 h, 92%; (b) HNO₃, CAN, DCM, 25 °C, 48 h, 92%; (c) HNO₃ (fuming), DCM, 0 °C, 20 min then rt, 12 h, 80–86%; (d) sulfur powder, DMF, 120 °C, 8 h; (e) sulfur powder, DMF, 120 °C, 6 h, 80%; (f) sulfur powder, DMF, 80 °C, 2 h, 80%; (g) sulfur powder, DMF, 120 °C, 3 h, 85%; (h) sulfur powder, NMP, 190 °C, 4 h, 82–86%; (i) sublimed sulfur, NMP, 110 °C, 10 h.

Scheme 62. Synthesis of Sulfur-Annulated Fused Perylene Diimides

Reagents and conditions: (a) sulfur powder, NMP, 70 °C then 62.1, 200 °C, 20 min.

Scheme 63. Synthesis of Dithiophene-Annulated Tetraarylperylenes

Reagents and conditions: (a) Pd(PPh₃)₄, bis(tributyltin)sulfide, toluene, reflux, 10 h; (b) 2-thienylmagnesium bromide, THF, 0 °C to rt, 12 h; (c) mesitylmagnesium bromide, THF, 0 °C to rt, 12 h.

Scheme 64. Synthesis of N-Annulated Thienoperylene Dyes

Reagents and conditions: (a) Amberlyst 15, toluene, reflux, 12 h; (b) t-BuLi, THF, −78 °C, 1 h, then chlorotrimethylstannane, −78 °C to rt, 24 h; (c) butyl 4-(7-bromobenzo[c][1,2,5]thiadiazol-4-yl)benzoate, Pd(PPh₃)₂Cl₂, toluene, reflux, 12 h; (d) KOH, 3:1 THF/H₂O, reflux, 8 h, then HCl. *64.2a and 64.3a were obtained in 1:2 ratio.

Scheme 65. Synthesis of N-Annulated Perylene Dyes

Reagents and conditions: (a) 4-hexylphenylmagnesium bromide, THF, reflux, overnight; (b) Amberlyst 15, toluene, reflux, overnight; (c) NBS, THF, 0 °C, 30 min; (d) butyl 4-(7-ethynylbenzo[c][1,2,5]thiadiazol-4-yl)benzoate, Pd₂(dba)₃, P(t-Bu)₃, Cs₂CO₃, dioxane, reflux, 5 h; (e) (1) KOH, 3:1 THF/H₂O, reflux, 8 h, (2) phosphoric acid.

Chart 5. N-Annulated Perylene Dyes

Scheme 66. Synthesis of a NAP–Triazine Hybrid

Reagents and conditions: (a)n-BuLi, THF, reflux, 5 h.

Scheme 67. Synthesis of N-Annulated Perylene Diimide Dimers

Reagents and conditions: (a) PPh₃, DMF, 150 °C, 21 h, 67%; (b) n-hexyl bromide, K₂CO₃, DMF, 120 °C, 18 h, 89–96% for 67.2a–b; (c) Br₂, DCM, rt, 2 h, 94–98%; (d) Pd(dba)₂, Zn dust, DMF, 100 °C, 3.5 h, 79–81%; (e) Br₂ (neat), rt, 1 h, 93%, then Pd(dba)₂, Zn dust, DMF, 120 °C, 30 min, 56%; (f) Boc₂O, DMAP, K₂CO₃, DMF, 80 °C, 24 h, 97%; (g) 200 °C, 1 h, quant. or 180 °C in thin films; (h) hexabutylditin, SiliaCat DPP-Pd, toluene, 100 °C, 1 h, 63%; (i) Zn dust, Pd₂(dba)₃, DMF, 100 °C, 2.5 h, 66%; (j) 67.6, Pd(PPh₃)₄, toluene, 180 °C, microwave, 10 min, 45%.

Chart 6. N-Annulated PDI Tetramers with Dimeric Cores

Scheme 68. Preparation of N-Annulated PDI Conjugates via Cross-Coupling Reactions

Reagents and conditions: (a) B₂pin₂, Pd(dppf)Cl₂, NaOAc, 10:3/1 DMF/toluene/H₂O, 70 °C, overnight, 49%; (b) Pd(PPh₃)₄, toluene, 100 °C, 24 h, 72%; (c) Pd(PPh₃)₄, K₂CO₃, 2:1 toluene/H₂O, reflux, 2 days, 41%.

Scheme 69. Synthesis of S- and Se-Annulated Perylene Diimide Dimers

Reagents and conditions: (a) CuI, l-proline, 110 °C, 24 h, 33%; (b) Br₂, H₂SO₄, rt, 2 days, 90%; (c) Cu, DMSO, 65 °C, 12 h, 76%; (d) (Bu₃Sn)₂S, Pd(PPh₃)₄, toluene, reflux, 12 h, 42%; (e) Zn dust, Pd₂(dba)₃, DMF, 55 °C, 1 h, 88%.

Scheme 70. Synthesis of N-Annulated Perylene Diimide Dimers with Acetylene Linkers

Reagents and conditions: (a) TMS-acetylene, Pd(PPh₃)₄, CuI, (i-Pr)₂NH, 40 °C, 24 h, then SiliaMetS DMT, DCM, rt, 4 h, 98%; (b) K₂CO₃, 1:1 CHCl₃/MeOH, rt, 10 min, 99%; (c) Pd(PPh₃)₄, CuI, 1:10 (i-Pr)₂NH/toluene, 60 °C, 0.3–5 h; (d) Pd(PPh₃)₄, CuI, K₂CO₃, 1:1 CHCl₃/MeOH, rt, air, 3 h, 71%.

Scheme 71. Preparation of Thiophene-Linked Dimeric N-Annulated PDIs via Direct Heteroarylation

Reagents and conditions: (a) SiliaCat DPP-Pd, PivOH, K₂CO₃, DMA, 80–90 °C, 24 h (or microwave, 80 °C, 4 h for 71f), 49–74%; (b) SiliaCat DPP-Pd, PivOH, Cs₂CO₃, DMA, 80 °C, 18 h, 34%; (c) Pd₂(dba)₃, P(o-Tol)₃, toluene, 80 °C, 36 h, 78%; (d) Pd(OAc)₂, pivalic acid, K₂CO₃, N,N’-dimethylacetamide, 80 °C, 24 h.

Scheme 72. Preparation of an N-Annulated PDI Dimer with a Fused Thiophene Bridge

Reagents and conditions: (e) FeCl₃, MeCN, toluene, 50 °C, 1 min, quant.

Scheme 73. Direct Heteroarylation Leading to Tetrameric N-Annulated PDI Conjugates

Reagents and conditions: (a) SiliaCat DPP-Pd, PivOH, K₂CO₃, DMA, 120 °C, 24 h, 70%; (b) SiliaCat DPP-Pd, AcOH, Cs₂CO₃, DMA, 120 °C, 24 h, 70%.

Scheme 74. Synthesis of Three-Dimensional Thiophene-Annulated PDI Dyes

Reagents and conditions: (a) Pd(PPh₃)₄, K₂CO₃, THF, reflux, 2 days, 81%; (b) Pd₂(dba)₃, P(p-C₆H₄OMe)₃, K₂CO₃, THF/H₂O, 16 h, reflux, 75%; (c) Pd(PPh₃)₄, K₂CO₃, 2:1 THF/H₂O, 80 °C, 2 days, 51–55%.

Scheme 75. Synthesis of Acceptors with Two, Three, and Four Se-Annulated Peryleneimide Units

Reagents and conditions: (a)^, Pd₂(dba)₃, P(o-tolyl)₃, toluene, reflux, 24 h, 70–85%.

Scheme 76. Synthesis of Vinylene- and Thiophene-Bridged S- and Se-Annulated PDI Dimers

Reagents and conditions: (a) Pd(PPh₃)₂Cl₂, toluene, reflux, 24 h, 77–80%; (b) I₂, toluene, hν (Hg lamp), 36 h, 55%.

Scheme 77. Synthesis of Benzene-Fused Se-Annulated PDI Dimers and Trimers

Reagents and conditions: (a) 1,3,5-benzenetriboronic acid tris(pinacol)ester, Pd(PPh₃)₄, Na₂CO₃, 2:1 THF/H₂O, reflux, 48 h, 91%; (b) I₂, toluene, hν (Hg lamp), rt, 24 h, 93%; (c) HNO₃ (fuming), DCM, rt, 12 h, quant.; (d) selenium powder, NMP, 190 °C, 12 h, 87%; (e) Pd(PPh₃)₄, K₂CO₃, 2:1 THF/H₂O, 85 °C, 13 h, 75%; (f) I₂, DCM, hν (sunlight), rt, 8 h, 80%; (g) ClSO₃H, rt, 4 h, quant.; (h) 6-undecylamine or 12-tricosylamine, imidazole, 150 °C, 4 h, 41%.

Scheme 78. Synthesis of Phenylene-Bridged Isomeric N-Annulated Perylene Diimide Dimers

Reagents and conditions: (a) Pd(OAc)₂, t-BuOK, P(t-Bu)₃, toluene, 110 °C, o/n, 47–54%.

Scheme 79. Chiral Twin N-Annulated Perylene Carboxamides

Reagents and conditions: (a) NBS, DMF, 0 °C, 30 min, 60%; (b) Pd(PPh₃)₄, K₂CO₃, 19:1 THF/water, reflux, 40 h, 49–80%; (c) Sc(OTf)₃, DDQ, toluene, rt, 22–48 h, 38–45%.

Chart 7. N-Annulated Perylenes with Amide-Bound Side Chains

Chart 8. Polymers Containing N-Annulated Perylene Units

Scheme 80. Synthesis of Benzoxepine-Fused Perylene Diimides

Reagents and conditions: (a) Cu(OAc)₂, Cs₂CO₃, PivOH, DMSO, 140 °C, overnight, 94%; (b) Pd(OAc)₂, PCy₃·HBF₄, K₂CO₃, DMA, 100–120 °C, 2–4 h (c) Pd(PPh₃)₄, Cs₂CO₃, paraformaldehyde, 1:1 DMF/toluene, 80 °C, 17 h, 97%.

Scheme 81. Benzyne Cycloaddition to Perylene Diimide

Reagents and conditions: (a) CsF, 1:1 toluene/MeCN, 80 °C, 36 h, 64%.

Scheme 82. Azabenzannulation of PDI by Cyclization with an Imine

Reagents and conditions: (a) (1) 3 equiv of R¹CHO, TFA, DCM, reflux, 3 h, (2) DCM, rt, hν (white LED), 1 h (12 h for 82.2c), (3) DDQ, DCM, rt, 2 min; (b) (1) 0.33 equiv of dialdehyde, TFA, toluene, reflux, 3 h, (2) DCM, rt, hν (white LED), 12 h, (3) DDQ, DCM, rt, 2 min.

Scheme 83. Coordination Chemistry of a Fused Perylenoid Ligand

Reagents and conditions: (a) TfOH, DMF, 110 °C, 2–3 h, 52–55%; (b) [Cp*IrCl₂]₂, 40 °C, 18 h, then NH₄PF₆, EtOH, 67%; (c) Ru(bpy)₂Cl₂, LiCl, AgClO₄, 20:7:1 CHCl₃/EtOH/Et₃N, 65 °C, 42 h, 69%; (d) [(ppy)₂IrCl]₂, 5:1 DCM/MeOH, 80 °C, 24 h, then NH₄PF₆, 2 h, 20%.

Scheme 84. Mechanochemical Cyclodehydrogenation of Polyarylpyridines

Reagents and conditions: (a) CoI₂, 1,3-bis(diphenylphosphino)propane, Zn, NMP, or DMA, 80 °C, 24 h; (b) K metal, ball milling (30 Hz), rt, 2 h.

Scheme 85. Synthesis of Pyridazine-Fused Perylenes

Reagents and conditions: (a) KMnO₄, 1:9 MeOH/H₂O, rt, 12 h, 87%; (b) N₂H₄·H₂O, EtOH, rt, overnight, 85%; (c) n-BuBr, NaOH, DMF, 60 °C, overnight, 40%.

Scheme 86. Synthesis of Twisted N-Doped Nanographenes

Reagents and conditions: (a)o-xylene, 80 °C, 30 min, then reflux, 12 h; (b) DDQ, TfOH, DCM (high dilution), 0 °C to rt, 4 h.

Scheme 87. Synthesis of Thiadiazole- and Triazole-Fused Perylenes

Reagents and conditions: (a) FeCl₃, MeNO₂, 0 °C, 3 h, 69–72%; (b) ArB(OH)₂, Pd(PPh₃)₄, K₂CO₃, 2:1 toluene/H₂O, 85 °C, overnight, 78–80%.

Scheme 88. Synthesis of Expanded Acridinium Cations

Reagents and conditions: (a) 1:25 conc. HCl_(aq)/AcOH, reflux, 36 h, 78%; (b) PbO₂, AcOH, reflux, 6.5 h, 77%; (c) HBF₄, 1:2 AcOH/MeCN, rt, 24 h, 93%; (d) 3,4,5-trimethoxyaniline, NMP, molecular sieves, reflux, 8 h, 38%; (e) MnO₂, HCl_(g), Ac₂O, reflux, 1 h, 66%; (f) 1:1 MeCN/H₂O, hν (sunlight), rt, 91%; (g) 4-(dimethylamino)phenylboronic acid, Pd(PPh₃)₄, Na₂CO₃, 5:8 DME/DMF, 95 °C, 24 h, 19%; (h) alkyne, Pd(PPh₃)₄, CuI, Et₃N, DMF, 80 °C, 30 h, 19%.

Scheme 89. Synthesis of Perylene Diimides Fused to Five-Membered Heterocycles

Reagents and conditions: (a) FeCl₃, MeNO₂, reflux, 3 h; (b) I₂, toluene, hν (incandescent lamp), air, rt, 24 h, 84%; (c) I₂, DCM, hν (xenon lamp), rt, 10 h, quant.; (d) FeCl₃, MeNO₂/chlorobenzene, 130 °C, 3 days, 66%; (e) FeCl₃, MeNO₂/toluene, 90 °C, 8 h, 37%.

Chart 9. Thienothiophene-Fused Perylene Diimides and Perylene Tetraesters

Chart 10. Further Examples of Dimeric Thiophene-Fused Perylene Diimides

Scheme 90. Synthesis of Tetrameric Thiophene-Fused PDIs

Reagents and conditions: (a) FeCl₃, 25:1 toluene/MeNO₂, rt, 2 h, 92%; (b) FeCl₃, 2:1 toluene/MeNO₂, 0 °C to rt, 5 h, 61%; (c) FeCl₃, 2:1 toluene/MeNO₂, 110 °C, 5 h, 65%.

Scheme 91. Synthesis and C–H Arylation of Thiazole-Annulated PDI

Reagents and conditions: (a) Pd(PPh₃)₄, CuI, 90 °C, 4 h, then I₂, hν (254 nm), rt, 3 h; (b) bis(chloro-di-tert-butylphosphine)palladium dichloride, Cu(Xantphos)I, K₂CO₃, DMF, 135 °C, overnight; (c) Ag₂O, Cu(Xantphos)I, K₂CO₃, DMF, 135 °C, overnight, 90%; (d) KOt-Bu, toluene, rt, 30 min, 94%; (e) Pd(PPh₃)₄, toluene, 110 °C, overnight, 90%.

Scheme 92. Synthesis of Isatin- and Isoindigo-Fused Perylene Diimides

Reagents and conditions: (a) Pd₂(dba)₃, P(t-Bu)₃·HBF₄, K₃PO₄, THF, 80 °C, 12 h; (b) I₂, CHCl₃, air, hν (sunlight), 25 °C, 24 h; (c) I₂, toluene, air, hν (blue LED), 90 °C, 12 h (flow reactor).

Scheme 93. Thiophene Imine-Fused Perylene

Reagents and conditions: (a) TfOH, DCM, rt; (b) oxone, 1:1 MeCN/H₂O, rt, 1 h.

Scheme 94. Synthesis of Benzimidazole-Fused Peryleneimides

Reagents and conditions: (a) 4,5-diaminophthalonitrile, Zn(OAc)₂, quinoline, 150 °C, 18 h, 45%; (b) 1,2-diaminoarene, imidazole, pyridine, 130 °C, 23 h, 43%; (c)o-phenylenediamine, propionic acid, reflux, 3 h, 87%.

Scheme 95. Synthesis of Dimeric Benzimidazole-Fused Perylenes

Reagents and conditions: (a) 1,2,4,5-tetraaminobenzene tetrahydrochloride, pyridine, reflux, overnight, 41%; (b) TsOH·H₂O, toluene, 110 °C, 24 h, 95%; (c) 1,2,4,5-tetraaminobenzene, ZnCl₂, quinoline, 170 °C, 18 h, 21%; (d) R¹NH₂, Zn(OAc)₂, imidazole, 140 °C, 2 h; (e) Zn(OAc)₂, quinoline, 145 °C, 14 h, 61%; (f) 1:1 H₂SO₄/propionic acid, 150 °C, 5 h, 89%.

Scheme 96. Polycondensation of 96.1

Reagents and conditions: (a) naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, m-cresol, 5 h at 80 °C then 32 h at 200 °C.

Scheme 97. Synthesis of Thiophene-Fused Perylenoids Through Dehydrogenative Photocyclizations

Reagents and conditions: (a) [Cu(OH)(Cl)(TMEDA)], DCM, air, rt, 1 h, 71%; (b) 2-naphthol, [Cu(OH)(Cl)(TMEDA)], DCM, air, rt, 2 h, 26%; (c) TsOH, toluene, reflux, 4 h; (d) CuI, PivOH, DMSO, 140 °C, 2 h.

Scheme 98. Synthesis of Pyridazine-Bridged Peryleneimide-thiophene Assemblies

Reagents and conditions: (a) AlCl₃, chlorobenzene, reflux, 6 h, 80% from 98.1a or 20% from 98.1b; (b) benzeneseleninic anhydride, chlorobenzene, 130 °C, overnight, 78–95%; (c) TsOH, CHCl₃, 50 °C, overnight.

Scheme 99. peri-Fused Perylenoids Bearing One or Two Boron Atoms

Reagents and conditions: (a) BBr₃, 2,4,6-tri-tert-butylpyridine, o-dichlorobenzene, heptane, rt, 24 h; (b) DCM, air, 1 h, then aq. HCl; (c) TipMgBr, o-dichlorobenzene, 48 h.

Scheme 100. Syntheses of Pyridine- and Thiophene-Fused Perylenes

Reagents and conditions: (a) KOt-Bu, THF, 60 °C, 16 h; (b) Me₃SI, sodium hydride, DMSO/THF, 50 °C, 1 h; (c) SnCl₂, 1,2-dichloroethane, 60 °C, 12 h.

Scheme 101. Synthesis of a Benzothiophene-Fused Perylene via Oxidative Cyclization

Reagents and conditions: (a) I₂, 4:3:4 CHCl₃/AcOH/propylene oxide, 55 °C, 12 h, 89%.

Scheme 102. Synthesis of π-Extended S-Doped Double [6]Helicenes

Reagents and conditions: (a) MoCl₅ (20 equiv), DCM (5 mM), rt, 40 min; (b) Pd/C, HCO₂H, Et₃N, pyridine, 130 °C, 25–72 h; (c) MoCl₅, O₂-purged dry DCM, rt, 27 h.

Scheme 103. Heteroannulation of Alkynyl-Substituted Perylene Diimides

Reagents and conditions: (a) sulfur powder, DMA, 140 °C, 20–48 h, 77–85%; (b) K₂S, DMF, 80 °C, 20–48 h; (c) selenium powder, DMA, 140 °C, 36 h, 62%; (d) benzylamine or n-butylamine, KOt-Bu, toluene, 4 Å MS, 120 °C, 18 h, 60–64%; (e) sulfur powder, 10:1 DMF/H₂O, 90 °C, 45 h, 9–10%; (f) TBAF, THF, rt, 1 h, 98%.

Scheme 104. Synthesis of Perylenodithiophenes and Their Dimers

Reagents and conditions: (a) sulfur powder, 10:1 DMF/H₂O, 90 °C, 12 h, 26–34%; (b) K₂CO₃, 10:1 THF/MeOH, rt, 3 h, 98%; (c) NBS, 20:1 DCM/AcOH, 55 °C, 79–80%; (d) Cu powder, DMSO, 90 °C, 10 h; (e) PdCl₂(dppf), TMEDA, NaBH₄, THF, 55 °C, 3 h, 45–66% (two steps).

Scheme 105. Stitching Thienannulations of Alkynyl-Substituted PDIs

Reagents and conditions: (a) K₂S, DMF, 170 °C, 12 h, 60%; (b) K₂S, DMF, 40 °C, 1 h, 63%; (c) K₂S, DMF, 105.5a: 80 °C, 2 days, 61%, 105.5b: 25 °C, 15 h, then 140 °C, 2 days, 79%.

Scheme 106. Synthesis of Thiophene-Fused Perylenoids Through Dehydrogenative Photocyclizations

Reagents and conditions: (a) Ac₂O, Et₃N, THF, reflux, 16 h, then 1-bromopropane, DBU, 1:10 PrOH/THF, reflux, 10 h, 53%; (b) I₂, 1:13 dioxane/toluene, hν (incandescent lamp), reflux, 6 days, 75%; (c) amine hydrochloride, imidazole, o-dichlorobenzene, reflux, 16 h, 33–40%; (d) Na₂CO₃, 77:1 acetone/H₂O, rt, hν (medium pressure mercury lamp), 5 h, 21%.

Scheme 107. Synthesis of Thiophene-Fused Perylenoids

R = t-Bu. Reagents and conditions: (a) [Rh(Cp*)Cl₂]₂, AgOAc, DMF, 100 °C, 16 h, 70%; (b) FeCl₃, 1:2 MeNO₂/DCM, rt, 1 h, 90%; (c) MeSO₃H, DDQ, DCM, 0 °C, 2 h, 49%.

Scheme 108. Cyclodehydrogenation toward Thiophene-Fused Nanographenes

Reagents and conditions: (a) PtCl₂, toluene, 100 °C, 20 h; (b) n-BuLi, THF, −78 °C, 1 h; (c) RB(pin), Pd(PPh₃)₄, K₂CO₃, toluene/EtOH/H₂O, 90–100 °C, 24 h; (d) DDQ, TfOH, DCM, −35 °C for 108.3a or 0 °C for 108.3b,c, 30–90 min.

Scheme 109. Reactions of PDIs and bay-Alkynyl PDI with DBU

Reagents and conditions: (a) DBU, toluene, 140 °C, 24 h, 26–32%; (b) DBU, toluene, 120 °C, overnight.

Scheme 110. Synthesis of Imidazole-Fused PDIs

Reagents and conditions: (a) NaNH₂, respective benzonitrile used as solvent, 150–170 °C, aeration, 0.5–3 h.

Scheme 111. Synthesis of Tetraindole- and Tetra(benzothiophene)-Fused PDIs

Reagents and conditions: (a)o-bromoaniline, KOt-Bu, neat, 120 °C, 24 h, 81%; (b) o-aminothiophenol, CuI, l-proline, Cs₂CO₃, CTAB, 3:1 toluene/H₂O, reflux, overnight, 97%; (c) Pd(OAc)₂, P(t-Bu)₃·HBF₄, Cs₂CO₃, DMF, 150 °C, 24 h, 51%; (d) isopentyl nitrite, 1:1 DCM/AcOH, 0 °C, 1 h, then hydroquinone, rt, 30 min, 70%.

Scheme 112. Synthesis of a Double Tetraoxa[7]helicene

Reagents and conditions: (a) DDQ, TfOH, DCM, 0 °C, 2 h.

Scheme 113. Azatriangulenetriones from Triarylamine Precursors

Reagents and conditions: (a) (1) KOH, MeOH/H₂O, (2) SOCl₂, DMF, then SnCl₄, DCM.

Chart 11. Benzamide-Functionalized Azatriangulenetrione Derivatives

Scheme 114. Azatriangulene Derivatives Bearing Peripheral sp³-Hybridized Carbon Atoms

Reagents and conditions: (a) Cu, CuI, K₂CO₃, n-Bu₂O, 150 °C, 48 h; (b) MeMgBr, toluene, 110 °C, 15 h; (c) 85% H₃PO₄, rt, 4 h; (d) tris(4-bromophenyl)ammoniumyl hexachloroantimonate (BAHA), DCM, N₂, rt, 1 h; (e) benzene, 80 °C, 24 h; (f) AcOH, H₂O, HCl, 100 °C, 12 h; (g) benzene/n-BuOH/pyridine, Dean–Stark apparatus, reflux, 5 h.

Scheme 115. Syntheses of Boron-Centered, Oxygen-Containing Heteratriangulenes

Reagents and conditions: (a) Pd(PPh₃)₄, K₂CO₃, toluene/EtOH/H₂O, reflux, 18 h; (b) aq. H₂SO₄ (2 M), THF, 50 °C, 3 days; (c) (1) n-BuLi, TMEDA, THF, 0 °C, 0.9 h, then rt, 4 h, (2) BF₃·Et₂O, THF/benzene, −40 °C, 0.4 h, then rt, 2 h, then 87 °C, 21 h; (d) BBr₃, DCM, −78 °C, 0.9 h, then rt, 2 h; (e) Tf₂O (2.1 equiv), i-PrNEt₂ (1.2 equiv), DCM, −78 °C, 1.25 h, then rt, 3 h; (f) DBU, DMF, microwave, 240 °C; (g) Tf₂O (2.2 equiv), i-PrNEt₂ (3.0 equiv), DCM, −78 °C, 1.25 h, then rt, overnight; (h) aniline, LiN(SiMe₃)₂, 1,4-dioxane, 10 °C, then 150 °C, 20 h.

Scheme 116. Phosphangulene Derivatives

Reagents and conditions: (a) Se, CDCl₃, rt, 25 days; (b) MeI, CDCl₃, 55 °C, 54 h; (c) BH₃·Me₂S, CDCl₃, rt, 10 min; (d) W(CO)₆, THF, preirradiated with a high-pressure mercury lamp (400 W) at rt for 30 min, then rt, 10 min; (e)^, Lawesson’s reagent, toluene, reflux. 12–16 h; (f) P(NMe₂)₃, toluene, reflux, 15–24 h; (g) (1) Br₂, 1,1,2,2-tetrachloroethane, 25 °C, 2 h, (2) NH₂OH·HCl, reflux, 20 h; (h) AgBF₄, DCM, 25 °C, 1 h; (i) [Cu(MeCN)₄]BF₄, DCM/MeCN, 25 °C, 12 h.

Scheme 117. Synthesis of Phosphorus-Centered, Sulfur-Containing Heteratriangulenes

Reagents and conditions: (a) dimethylthiocarbamoyl chloride, DABCO, DMF, rt, 30 min, then 75 °C, 2–17 h; (b) 240 °C, argon, 2–5 h; (c) t-BuOK, DMF, 140 °C, 21 h; (d) SiHCl₃, Et₃N, toluene, 120 °C, 61–72 h.

Scheme 118. Divergent Synthesis of the Heteroatom-Centered 4,8,12-Triazatriangulenes

Reagents and conditions: (a)t-BuLi, t-butylbenzene, −45 °C, then 50 °C, 30 min to 2 h; (b) BBr₃, i-Pr₂NEt, −45 °C, 1 h, then 165 °C, 14 h; (c) MeSiCl₃, t-butylbenzene, 150 °C, 18 h; (d) (1) PCl₃, toluene, 50 °C, 2 h, (2) S₈, o-dichlorobenzene, 110 °C, 12 h; (e) m-CPBA, DCM, −30 °C, 1 h; (f) PEt₃, o-xylene, 120 °C, 2 days.

Chart 12. Diboratriangulenes

Scheme 119. π-Extended Dioxa- and Diazadioxatriangulene

Reagents and conditions: (a) CuO, nitrobenzene, air, reflux, overnight; (b) TFA, toluene, O₂, 100 °C, 16 h.

Scheme 120. Synthesis of the Triazatriangulene Derivatives Bearing Different Axial Groups at the Central Carbon Atom

Reagents and conditions: (a)n-BuLi, THF, 0 °C, 1 h then rt, 1 h, (2) [120.1][BF₄], rt, overnight; (b) (1) KOH powder, THF, 0 °C, 30 min, (2) [120.1][BF₄], 0 °C.

Scheme 121. Lewis Acid–Base Chemistry of a Trioxatriangulenium Cation

Reagents and conditions: (a) MeCN (for a–c), CDCl₃ or CD₃CN (for d), CD₂Cl₂ or CD₃CN (for e), rt, 5 min; (b) 1,3-di-t-butylimidazol-2-ylidene, toluene, rt, 1 h; (c) 1,3-di-t-butylimidazol-2-ylidene, toluene, −78 °C, 30 min.

Chart 13. Diazaoxa- and Azadioxatriangulenium Salts

Scheme 122. Diheteratriangulenium Dyes with an Isopropylene Bridge

Reagents and conditions: (a)m-dimethoxybenzene, TMEDA, n-BuLi, 1:1 benzene/Et₂O, 0 °C to rt, 3 h; (b) pyridine hydrochloride, 190–200 °C; (c) 2 equiv of methylamine, PhCO₂H, NMP, 70 °C, 3 days; (d) 60 equiv of methylamine, PhCO₂H, 1:1 EtOH/NMP, reflux, 5 days.

Scheme 123. Construction of π-Extended Diazapyrenoids by Annulation

Reagents and conditions: (a) Cu(OAc)₂ (20 mol %), Cs₂CO₃ (1.0 equiv), dioxane, O₂, 100 °C; (b) dioxane, rt, 6 h; (c) K₂CO₃, THF, 85 °C, 8 h; (d) THF, 80 °C, 36 h; (e) p-phenylenediamine, CHCl₃, rt, several seconds; (f) PbO₂, CHCl₃, 45 °C, 5 h.

Scheme 124. Diaza- and Tetraazapyrenoids from Condensation of Ketone Precursors

Reagents and conditions: (a) aq. HCl, reflux, 24 h; (b) (1) Na₂S₂O₄, NaOH, H₂O, 60 °C, 1 h, (2) C_nH_2n+1Br, Aliquat 336, toluene, 90 °C, 24 h; (c) (1) 2-octylthiophene and n-BuLi (premixed in Et₂O at −78 °C for 1.5 h), −78 °C, then rt, overnight, (2) SnCl₂·H₂O, rt, 3 h; (d) MsOH, 150 °C, 16 h; (e) (1) NaH, DMF, rt, 2 h, (2) EtI, rt, 24 h; (f) N₂H₄·H₂O, EtOH, 130 °C, 72 h; (g) toluene, 120 °C, 48 h.

Scheme 125. Cationic Azapyrenoids

Reagents and conditions: (a) (1) KOH, EtOH, 0 °C, rt, 26 h, (2) NH₂OH·HCl, reflux, 2 h; (b) 5% HCl, hν (300 nm), air, rt, 24 h; (c) (1) MeI or RBr, DMF, 100 °C, 48 h, (2) KPF₄, H₂O, rt; (d) I₂, pyridine/1,4-dioxane, rt, 12 h; (e) TCNQ, MeCN, reflux, 20 h; (f) 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, MeCN, reflux, overnight; (g) (1) DMF, argon, 60 °C, 2 h, (2) toluene, Dean–Stark apparatus, 140 °C, 6 h; (h) (1) MeCN, O₂, hν (300–400 nm), 14 h, (2) NH₄PF₆; (i) Fe(acac)₃, AcOH, 90 °C, 12 h; (j) MeOTf, 1,2-DCE, 50 °C, 16 h; (k) Et₃N, MeCN/DCM, argon, rt, 2 h.

Scheme 126. Benzimidazole-Fused Carbonyl-Containing Pyrenoids

Reagents and conditions: (a) H₂O, 180–250 °C, autoclave or microwave reactor.

Scheme 127. Imidazole-Fused Pyrene via Oxidative Coupling

Reagents and conditions: (a) PIFA, BF₃·Et₂O, toluene, rt.

Scheme 128. B,N-Doped Pyrenoids

Reagents and conditions: (a) BBr₃, i-Pr₂EtN, o-DCB, 180 °C; (b) PhBCl₂, Et₃N, 1,2,4-trichlorobenzene, reflux, 36 h; (c) Pd(OAc)₂, PCy₃, Cs₂CO₃, o-xylene, reflux, overnight.

Scheme 129. Synthesis of BN-Doped Pyrenoids

Reagents and conditions: (a) 2 equiv of BBr₃, toluene, reflux, 20 h; (b) 4 equiv of BBr₃, chlorobenzene, reflux, 20 h; (c) 12 equiv of BBr₃, benzene, reflux, 20 h; (d) 24 equiv of BBr₃, chlorobenzene, reflux, 20 h; (e) 1 equiv of BBr₃, o-dichlorobenzene, 170 °C, 20 h.

Scheme 130. Benzimidazole-Fused π-Systems Derived from Naphthalene Monoimide Monoanhydride

Reagents and conditions: (a)^, (1) Et₃N, quinoline, rt, 30 min, (2) 130.2a/b, Zn(OAc)₂, 180 °C, overnight.

Scheme 131. Synthesis of C_s- and C_3v-Symmetric π-Extended Triptycene Derivatives

Reagents and conditions: (a)^, Zn(OAc)₂·2H₂O, quinoline, 180 °C, 24 h; (b) SnCl₂·2H₂O, EtOAc, 85 °C, 12 h; (c) DMF (for a) or Zn(OAc)₂·2H₂O, quinoline (for b and c), 140 °C, 72 h.

Scheme 132. Fused Xanthenes via Alumina-Promoted Oxodefluorination

Reagents and conditions: (a) γ-Al₂O₃, 190 °C, 12 h.

Scheme 133. Synthesis of Pyrylium-Fused Oxapyrenes

Reagents and conditions: (a) [Cp*RhCl₂]₂, Cu(OAc)₂, NaBF₄, THF, 150 °C, 24 h.

Scheme 134. Synthesis of Zig-Zag O-Doped peri-Acenoacenes

Reagents and conditions: (a) CuCl₂, 1-phenylethan-1-amine, MeOH, DCM, 0 °C to rt, 2 h; (b) CuI, pivalic acid, DMSO, 130 °C, 2 h; (c) CuCl, K₂CO₃, N-methylimidazole, 120 °C, 20 h, 64%; (d) n-dodecanethiol, NaOH, NMP, 130 °C, 4 h, 93%; (e) Cu-TMEDA, DCM, rt, 5 min; (f) CuCl, K₂CO₃, N-methylimidazole, 120 °C, 20 h.

Scheme 135. Synthetic Strategies Toward the Preparation of peri-Xanthenoxanthene Imides

Reagents and conditions: (a)^, Br₂, dioxane, reflux, 2.5 h; (b) i-Pr₂NEt, n-octylamine, dioxane, reflux, 16–24 h; (c) K₂CO₃, CH₃I, MeCN, reflux, 4 h; (d) Cs₂CO₃, B₂Pin₂, Pd(dba)₂, SPhos, dioxane, reflux, 18 h; (e) BBr₃, DCM, 0 °C to rt, 16 h; (f) pivalic acid, CuI, DMSO, 120 °C, 5 h; (g) DBU, MeI, MeOH, reflux, 18 h; (h) B₂Pin₂, KOAc, Pd(PPh₃)₂Cl₂, 1,4-dioxane, reflux, 16 h; (i) 135.6a, 135.6b, K₃PO₄, Pd(dba)₂, SPhos, 1,4-dioxane, H₂O, reflux; (j) (1) KOH, i-PrOH, reflux, 13 h, (2) HCl(aq.), AcOH, reflux, 24 h; (k) HBr(aq.), AcOH, 126 °C, 24 h; (m) CuCl, DMSO, 120 °C, 24 h, air.

Scheme 136. Synthesis of π-Radical Cation [136.4]^•+

Reagents and conditions: (a) s-BuLi, TMEDA, THF, −78 °C, 45 min, then phenalenone, −78 °C to rt, overnight; (b) TfOH, 1,1,2,2-tetrachloroethane, 120 °C, 12 h; (c) Na₂S₂O₄, MeCN, rt, 2 h.

Chart 14. Xylindein

Scheme 137. Synthesis of a Screw-Shaped Polymer

Reagents and conditions: (a) K₂CO₃, diphenyl sulfone, 210 °C, 5 h; (b) (1) H₂SO₄, 160 °C, 6 h, (2) tetrabutylammonium iodide, 120 °C, 6 h.

Scheme 138. Synthesis of Dithiapyrenoids and Pyrene-Containing Thioxanthene

Reagents and conditions: (a) phenylboronic acid neopentylglycol ester, [Cp*Rh(MeCN)₃][SbF₆]₂, Ag₂O, t-AmOH, 120 °C, 48 h; (b) (1) m-CPBA, DCM, rt, (2) TfOH, 1,2-DCE, rt, (3) pyridine, water; (c) I₂, CHCl₃, 1 h at 70 °C, 1 h at 80 °C, 22 h at 90 °C.

Scheme 139. Synthesis of Polycyclic Conjugated Arylboranes

Reagents and conditions: (a) PPh₃Ru(cymene)Cl₂, NH₄PF₆, 1,2-DCE, 75 °C; (b) (1) neat BBr₃, rt, (2) MesMgBr, THF, rt; (c) I₂, hν, toluene, rt; (d) PPh₃Ru(cymene)Cl₂, NH₄PF₆, 1,2-DCE, 80 °C.

Scheme 140. π-Extended Bora- and Diborapyrenes from Alkynes

Reagents and conditions: (a) (1) BCl₃, 2,4,6-tri-tert-butylpyridine, DCM, 5 min, (2) AlCl₃, 15 min; (b) AlCl₃, 2,6-dichloropyridine, DCM, 18 h; (c) [Ph₃C][BF₄], 2,4,6-tri-tert-butylpyridine, DCE, 75 °C, 120 h; (d) toluene, rt, overnight; (e) Sc(OTf)₃, DCE, 75 °C, 16 h; (f) TipMgBr, toluene, overnight.

Scheme 141. Oxygen-Doped Pyrenoids via Oxidative Pummerer Cyclization

Reagents and conditions: (a) BBr₃, DCM, 0 °C to rt, overnight; (b) CuO, nitrobenzene, 240 °C, overnight.

Scheme 142. Triflic-Acid-Promoted Cyclization of Thioamide S-Oxides

Reagents and conditions: (a) TfOH, DCM, rt.

Scheme 143. Synthesis of Thiopyrylium-Fused Pyrene

Reagents and conditions: (a) Cu₂O, 2,4,6-trimethylpyridine, 150 °C, 48 h, 59%; (b) TfOH, DCM, rt, 2 h, 64%.

Scheme 144. Vicinal Diborylation Reaction toward Doubly Boron-Doped Polycyclic Arenes

Reagents and conditions: (a) (1) BBr₃, n-hexane, ampule flame-sealed under vacuum, 120 °C, 2.5 days, (2) MesMgBr, toluene/THF, 0 °C, then rt, overnight.

Scheme 145. Synthesis of a Benzo[4,5]thieno[3,2-b]pyridine-Fused Pyrene

Reagents and conditions: (a) [Cp*IrCl₂]₂, AgSbF₆, Ag₂O, Zn(OTf)₂, hexafluoroisopropanol, 140 °C, 24 h.

Scheme 146. One-Pot Synthesis of an [a]-Thiophene-Fused Pyrene

Reagents and conditions: (a) (1) 146.5, triflic anhydride, DCE, −30 to 90 °C, MW heating, (2) Et₃N, 0 to 50 °C; (b) DDQ, toluene, rt to 80 °C; (c) (1) 146.6, triflic anhydride, DCE, −30 to 90 °C, MW heating, (2) Et₃N, 0 to 50 °C.

Scheme 147. Synthesis of TIPS-Substituted Thieno-Fused Anthanthrenes and Pyrenes

Reagents and conditions: (a) polyphosphoric acid, 90–120 °C, 24 h; (b) (1) triisopropylsilylacetylene, n-BuLi, THF, 0 °C, 1 h then 147.2, rt, 6 h, (2) SnCl₂·2H₂O, HCl, rt, 3 h; (c) TfOH, MsOH, 140 °C, 4 h; (d) (1) triisopropylsilylacetylene, n-BuLi, Et₂O, 0 °C, 1 h, then 147.6 or 147.9 in THF, rt, overnight, (2) SnCl₂·2H₂O, HCl, rt, 1 h.

Scheme 148. Synthesis of a Dithiophene-Fused Benzopyrene

Reagents and conditions: (a) FeCl₃, MeNO₂, 0 °C, 10 min for 148.2a or 1 h for 148.2b.

Scheme 149. Synthesis of Iridium Complexes Containing Phenanthro[4,5-abc]phenazino[11,12-d]imidazol-2-ylidene

Reagents and conditions: (a)^,149.7, MeOH, reflux, overnight; (b) NH₄PF₆, MeOH/DCM (3:1), rt, overnight; (c) potassium tert-butoxide, NaI (in the case of 149.3a,b), [IrCl(cod)]₂, THF, rt, overnight; (e) CO, DCM, 0 °C, 20 min; (d) potassium tert-butoxide, [IrCl(cod)]₂, KI (in case of 149.6c), THF, rt, overnight.

Scheme 150. Synthesis of a Pyrene-Fused N-Heteroacene

Reagents and conditions: (a) (1) CHCl₃/AcOH (2:1), 80 °C, 36 h, (2) MnO₂, DCM; (b) CHCl₃/AcOH (2:1), 80 °C, 30 h; (c) LiAlH₄, THF, 0 °C to rt, 14 h; (d) CHCl₃/AcOH (4:1), 80 °C, 48 h.

Scheme 151. Synthesis of Di- and Tetracyanopyrazines

Reagents and conditions: (a) 2,3-diaminomaleonitrile, EtOH/AcOH (1:1), 80 °C, 11–16 h; (b) 4,5-diaminophthalonitrile, EtOH/AcOH (1:1), 80 °C, 11–16 h.

Scheme 152. Synthesis of Unsymmetrically Fused Pyrazaacenes

Reagents and conditions: (a) 1,2-diamino-4,5-didodecyloxybenzene, AcOH, CHCl₃, reflux; (b) AcOH, reflux.

Scheme 153. Synthesis of Thiophene-Substituted Pyrazine-Fused Pyrenoids

Reagents and conditions: (a) AcOH, 100 °C, 24 h.

Scheme 154. Synthesis of Thiadiazoloquinoxaline-Containing Long Pyrene-Fused N-Heteroacenes

Reagents and conditions: (a)150.1/150.4 (1:1), CHCl₃/AcOH (2:1), reflux, 1 day; (b)150.1/150.4 (1:2), CHCl₃/AcOH (1:1), 80 °C, 1 day; (c)150.1/150.4 (1:1), CHCl₃/AcOH (1:1), reflux, 1 day; (d)150.1/150.4 (1:2.9), AcOH, 132 °C, overnight; (e)150.1/154.1 (1:3), AcOH, reflux, overnight; (f) LiAlH₄, THF, 0 °C to rt, overnight; (g)154.2, CHCl₃/AcOH (1:1), reflux, 1 day; (h) CHCl₃/AcOH (1:1), reflux, 1 day.

Chart 15. Pyrene-Fused Azaacenes

Scheme 155. Synthesis of Triptycene End-Capped Quinoxalinophenanthrophenazines

Reagents and conditions: (a) KOAc, CHCl₃, AcOH, 70 °C, 16 h; (b)155.1, KOAc, CHCl₃, AcOH, 70 °C, 16 h; (c)o-phenylenediamine, CHCl₃, AcOH, 70 °C, 16 h; (d) appropriate o-phenylenediamine, CHCl₃, AcOH, 70 °C, 16 h; (e) NMP, CuCN, 180 °C 15 h.

Chart 16. Quinoxalino–Phenanthrophenazine-Fused Tribenzotriquinacenes

Scheme 156. Synthesis of Triptycene-Based Three-Dimensional Pyrene-Fused N-Heteroacenes

Reagents and conditions: (a) KOAc, AcOH, chlorobenzene, reflux, 2 days; (b) LiAlH₄, THF, 0 °C to rt; (c) 156.2, KOAc, AcOH, chlorobenzene, reflux, 2 days; (d) (1) LiAlH₄, THF, 0 °C to rt, (2) 156.2, KOAc, AcOH, chlorobenzene, reflux, 2 days.

Scheme 157. Dimeric Cycloparaphenylenes with a Rigid Aromatic Linker

Conformations interconvert at rt.

Scheme 158. Iterative Synthesis of Pyrazine-Containing Nanoribbons

Reagents and conditions: (a) CHCl₃, AcOH, reflux, 48 h; (b) TFA, water, rt; (c) CHCl₃, AcOH, reflux, 4 days; (d) (1) TFA, water, rt, (2) CHCl₃, AcOH, reflux, 3 days.

Scheme 159. Synthesis of Azaacenes Containing BN Units

Reagents and conditions: (a) BF₃·Et₂O, Et₃N, DCM, 50 °C; (b) malononitrile, Al₂O₃, toluene, reflux, 12 h.

Scheme 160. Synthesis of Pyrene-Fused Azaacene Dimers

Reagents and conditions: (a) CHCl₃, AcOH, reflux; (b) p-diiodobenzene, PdCl₂(dppf), K₃PO₄, THF, H₂O, 80 °C, 11 min, microwave heating; (c) m-diiodobenzene, PdCl₂(dppf), K₃PO₄, THF, H₂O, 80 °C, 11 min, microwave heating; (d) o-diiodobenzene, PdCl₂(dppf), K₃PO₄, THF, H₂O, 80 °C, 11 min, microwave heating.

Scheme 161. Synthesis of Poly(2,11-diquinoxalinopyrene)

Reagents and conditions: (a) (1) bis(1,5-cyclooctadiene) nickel(0), 1,5-cyclooctadiene, 2,2′-bipyridine, DMF, 85 °C, 30 min, (2) 161.1b in toluene, 12–48 h, (3) bromobenzene, 4 h.

Scheme 162. Synthesis of Thiophene- and Pyrazaacene-Based Oligomers

Reagents and conditions: (a) Pd(PPh₃)₂Cl₂, toluene, 100 °C, 48 h, 162.2/162.3/162.4 were used in molar ratios of 0.5:2:1, 0.25:2:1.5, and 0.125:2:1.75 for 162.5a, 162.5b, and 162.5c, respectively; (b) Pd(PPh₃)₂Cl₂, toluene, 100 °C, 48 h, 162.2/162.1/162.4 were used in molar ratios of 0.5:2:1, 0.25:2:1.5, and 0.125:2:1.75 for 162.6a, 162.6b, and 162.6c, respectively.

Scheme 163. Synthesis of Pyrene-Fused Pyrazaacenes on Metal Surfaces

Reagents and conditions: (a) Ag(111), T_STM = rt to 510 K, U_s = 2.22 V, I_t = 0.09 nA.

Chart 17. Symmetric Heteroacenes and Pyrazine-Fused Pyrenoids

Chart 18. Unsymmetrical Pyrazaacenes

Chart 19. Mechanically Interlocked Nitrogenated Nanographenes

Scheme 164. Synthesis of the Pyridazine- and Pyrrole-Extended Pyrenes

Reagents and conditions: (a) N₂H₅OH, pyridine, water, reflux, 3 h; (b) Zn, DCM, AcOH, rt, 3 h; (c) HCOONH₃CH₃, 145 °C, 24 h.

Scheme 165. Syntheses of Pyrenoimidazole Derivatives

Reagents and conditions: (a) 4-R-benzaldehyde (R = H, OCH₃, CN, CF₃, NO₂, or CO₂CH₃), NH₄OAc, AcOH, reflux, 24 h; (b) [RuCl₂(p-cymene)]₂, 1-adamantanecarboxylic acid, Cu(OAc)₂, K₂CO₃, diphenylacetylene, 120 °C, 16 h; (c) 4-tert-butylaniline, 2-iodobenzaldehyde, NH₄OAc, AcOH, 110 °C, 5 h; (d) hν, 48–72 h; (e) benzaldehyde, NH₄OAc, dioxane, 120 °C, 3 days; (f) aniline, benzaldehyde, NH₄OAc, AcOH, reflux, 2 h.

Scheme 166. Pyrene-Fused Imidazolium Cations and Their NHC Complexes

Reagents and conditions: (a) (1) NaOH, DMSO, rt, 2 h, (2) RBr or RI (2 equiv), rt for 30 min, then 37 °C, overnight; (b) (1) NaOH, DMSO, rt, 2 h, (2) RBr or RI (excess), rt for 30 min, then 37 °C, overnight; (c) MeI (excess), 100 °C, 24 h; (d) [Pt(ppy)(μ-Cl)]₂, (ppy = 2-phenylpyridinate), NaOAc, NaI, DMSO, 100 °C, overnight; (e) (1) AgBF₄, DCM, 1 h, (2) NaCN, rt, overnight. For 166.2eanti and syn isomers were obtained as a mixture in 1:1 ratio and were not separated. Total yield is given. Isomers 166.5a and 166.6a were obtained as a mixture in 6:4 ratio and were not separated. Total yield is given. 166.5b and 166.6b were obtained as a mixture in 1:1 ratio and were not separated. Total yield is given.

Scheme 167. Synthesis of the Pyrene-Biimidazole-Based Ru(II) and Os(II) Complexes

Reagents and conditions: (a) (1) cis-[Ru(bpy)₂Cl₂]·2H₂O, AgClO₄, EtOH, reflux, 1 h, (2) 167.1, reflux, 10 h; (b) (1) cis-Os(bpy)₂Cl₂, EtOH, water, reflux, 40 h, (2) NaClO₄, rt; (c) (1) cis-[Ru(bpy)₂Cl₂]·2H₂O, ethylene glycol, reflux, overnight, (2) NaClO₄, water, rt; (d) (1) cis-Os(bpy)₂Cl₂, ethylene glycol, reflux, overnight, (2) NaClO₄, water, rt.

Scheme 168. Synthesis of Pyrenodiimidazole Polymers

Reagents and conditions: (a) 5-Bromothiophene-2-carbaldehyde, NH₄OAc, AcOH, reflux, 10 h; (b) 1-bromooctadecane, DMF, 100 °C, 12 h; (c) Pd(PPh₃)₄, THF, 65 °C, 16–20 h.

Scheme 169. Self-Condensation of Pyrene-4,5-dione

Reagents and conditions: (a) NH₄OAc, AcOH, 100 °C.

Scheme 170. Synthesis of the Pyridazine-Extended Pyrenes

Reagents and conditions: (a) N₂H₅OH, pyridine, water, reflux, 3 h; (b) N₂H₅OH, MeOH, 70 °C, 72 h.

Scheme 171. Synthesis of Chiral Pyrene-Based Compounds

Reagents and conditions: (a) (R)- or (S)-(±)-2,2′-diamino-1,1′-binaphthalene, CF₃COOH, toluene, 60 °C, 3 h; (b) AcOH, reflux, overnight.

Scheme 172. Synthesis of Unsymmetrical Azatwistacenes

Reagents and conditions: (a) P(OEt)₃, o-DCB, 160 °C, 24 h; (b) aniline, Pd(OAc)₂, PCy₃, t-BuOK, toluene, reflux, 48 h; (c) NaN₃, CuI, N,N′-dimethylethylenediamine, DMSO, 120 °C, 48 h; (d) (1) n-BuLi, THF, −78 °C, 2 h, (2) dimesitylboron fluoride, rt, 24 h.

Scheme 173. Synthesis and Reactivity of Furan-Extended Pyrenes

Reagents and conditions: (a) LiAlH₄, Et₂O, rt, 30 min; (b) NaBH₄, MeOH, rt, overnight; (c) CsF, MeCN/THF, 40 °C, overnight.

Scheme 174. Synthesis of Oxygen- and Nitrogen-Doped Twistacenes

Reagents and conditions: (a) 1-naphthol, PPh₃, Cs₂CO₃, Pd(OAc)₂, DMF, 140 °C, 24 h; (b) catechol, NaH, NMP, 205 °C, 12 h; (c) 2-aminophenol, NaH, NMP, 205 °C, 12 h; (d) K₂CO₃, DMF, 110 °C.

Scheme 175. Synthesis of Oxatwistacene

Reagents and conditions: (a) (1) I₂, DCM, (2) n-BuLi, THF; (b) I₂, DCM; (c) Pd(OAc)₂, K₃PO₄, 2-di-t-butylphosphino-2′-methylbiphenyl, toluene, 100 °C, 24 h.

Scheme 176. Synthesis of a Twelve-Ring Twistheteroacene

Reagents and conditions: (a) K₂CO₃, DMF.

Scheme 177. Synthesis of Thiophene and Selenophene Extended Pyrenes

Reagents and conditions: (a) P₄S₁₀, NaHCO₃, MeCN, reflux, 20 h; (b) Lawesson’s reagent, reflux, overnight, in the dark; (c) Woollins’ reagent, reflux, 2 h, in the dark.

Scheme 178. Synthesis of Thiophene- and Benzothiophene-Fused [e]-Pyrene

Reagents and conditions: (a) I₂, MeCN, UV light irradiation, rt, 130 h (178.1a), 30 h (178.1b), 150 h (178.1c); (b) iron(III) chloride, nitromethane, 0 °C, 1.5 h; (c)^, I₂, benzene, hν.

Scheme 179. Annulative Dimerization of Phenylene Triflate

Reagents and conditions: (a) PdCl₂, P(n-Bu)₃·HBF₄, K₂CO₃, pivalic acid, cyclopentyl methyl ether, 140 °C, 20 h; (b) FeCl₃, DCM, 0 °C, 2.5 h. * Obtained as a mixture of two regioisomers 179.2a and 179.2b in 4:1 ratio (overall yield). ** n.d. = not determined. Obtained as a complex mixture.

Scheme 180. Synthesis of Sulfur-, Selenium-, and Nitrogen-Doped Twistacenes

Reagents and conditions: (a) toluene-3,4-dithiol, K₂CO₃, DMF, 100 °C, 1 h; (b) 2-aminobenzenethiol, K₂CO₃, DMF, 130 °C, 1 h; (c) Na₂S·9H₂O, NMP, 195 °C, overnight; (d) (1) Se, sodium borohydride, EtOH, 0 °C, 40 min, (2) 180.3 in NMP, then 190 °C, overnight.

Scheme 181. S-Doped Hexacene via Nucleophilic Substitution

Reagents and conditions: (a) 1,2-benzenedithiol, K₂CO₃, DMF, reflux, 12 h; (b) NO{Al[OC(CF₃)₃]₄} (1 equiv), toluene, rt, 12 h; (c) NO{Al[OC(CF₃)₃]₄} (2 equiv), DCM, rt, 12 h.

Scheme 182. Synthetic Route of Bisphenaleno-thieno[3,2-b]thiophene

Reagents and conditions: (a) (1) SOCl₂, dry DCM, reflux, (2) AlCl₃, dry DCM, 0 °C to rt, overnight; (b) (1) (triisopropylsilyl)ethynyllithium, THF, 0 °C to rt, (2) SnCl₂, toluene, rt, 12 h.

Scheme 183. Syntheses of Azabenzophenalenoids

Reagents and conditions: (a)t-BuONa, Pd(OAc)₂, Pd₂(dba)₃, Cy₃P, (t-Bu)₃P, toluene, 90 °C, 10 h.

Scheme 184. Reactivity of 4-Amino-5-hydrazineyl-4h-1,2,4-triazole-3-thiol

Reagents and conditions: (a) glacial acetic acid, reflux, 4 h.

Scheme 185. Byproduct Formation in the Synthesis of a Tribenzosubporphyrin

Reagents and conditions: (a) B(OH)₃, 360 °C.

Scheme 186. Synthesis of Nitrogen-Containing Phenalenoids via Rhodium-Catalyzed Multiple C–H Bond Activation and Oxidative Annulation

Reagents and conditions: (a) [Cp*RhCl₂]₂, Cu(OAc)₂, DMF, 100 °C, Ar, 24 h.

Scheme 187. N-Doped Heptazethrene and Octazethrene

Reagents and conditions: (a) Pd(PPh₃)₄, 2 M Na₂CO₃, 1,2-dimethoxyethane, 115 °C, 48 h; (b) BBr₃, dry DCM, rt, 48 h; (c) hydrazine monohydrate (80%), DMSO/i-PrOH, 140 °C, 72 h; (d) PbO₂, dry DCM, rt, 30 min.

Scheme 188. Polycyclic Heterahelicenes

Reagents and conditions: (a) (1) bis(4-tert-butylphenyl)amine, Cu, 18-crown-6, K₂CO₃, 200 °C, 24 h, (2) NaOH, EtOH, 100 °C, 9 h; (b) (1) (COCl)₂, DMF, DCM, 45 °C, 1 h, (2) SnCl₄, 45 °C, 12 h; (c) MesLi, THF, −15 °C to rt, 18 h; (d) Et₃SiH, HBF₄·Et₂O, DCM, rt; (e) NaH, THF/hexane, rt, 4 h.

Scheme 189. Synthesis of a Ceramidonine via a Copper Trifluoroacetate-Mediated Relay Reaction

Reagents and conditions: (a) Cu(OTf)₂, 1,1,2,2-tetrachloroethane (TCE), 100 °C, 60 h.

Scheme 190. Synthesis of Planar Acridinone Heterocyclics

Reagents and conditions: (a) Cu(OAc)₂ (2 equiv), AcOH (1.8 equiv), o-DCB, 140 °C, under air, 24 h; (b) DCM, 80 °C, reflux, overnight; (c) (1) toluene, 180 °C, 16 h, (2) p-TsOH, 8 h, 180 °C; (d) 10 mol % of Pd(AcO)₂, Cu(AcO)₂, O₂, TFE, 120 °C, 24 h.

Scheme 191. π-Extended Acridones

Reagents and conditions: (a) BF₃·Et₂O, hν, rt, 1 h.

Scheme 192. Synthetic Routes to 8-Borabenzo[gh]tetraphenes

Reagents and conditions: (a) excess neat BBr₃, 25 °C; (b) 1.5 equiv of MesLi, toluene/THF, 0 °C; (c) 1.1 equiv of [2,6-bis(propen-2-yl)phenyl]lithium, toluene/THF, 25 °C; (d) 1 equiv of Sc(OTf)₃, 1,2-DCE, reflux temperature.

Scheme 193. Synthetic Routes to Boron-, Nitrogen-, and Sulfur-Doped PAHs

Reagents and conditions: (a)n-BuLi, Et₂O; (b) UV irradiation (Hg medium pressure lamp), I₂, propylene oxide, cyclohexane; (c) (1) excess neat BBr₃, (2) MesMgBr, toluene/THF; (d) (1) [n-Bu₄N]F, THF, (2) (PPh₃)Ru(cymene)Cl₂, NH₄PF₆, (CH₂Cl)₂.

Scheme 194. One-Pot Synthetic Routes to B-Doped PAHs

Reagents and conditions: (a) (1) BBr₃, TBP, TCB, 200 °C, 24 h, (2) MesMgBr, rt, 1 h.

Scheme 195. Photocyclization Reactions of Arylphenols

Reagents and conditions: (a)hν, deoxygenated H₂O/CH₃CN; (b) Pd/C, O₂, toluene.

Scheme 196. Synthesis of Pyridinium-Fused Oxaphenalenes

Reagents and conditions: (a) [Cp*RhCl₂]₂, Cu(OAc)₂, THF, 100 °C, 12 h; (b) [Cp*RhCl₂]₂, Cu(OAc)₂, NH₄BF₄, THF, 150 °C, 24 h.

Scheme 197. π-Extended Thiaphenalenoids

Reagents and conditions: (a) [Cp*RhCl₂]₂ (5 mol %), AgSbF₆ (20 mol %), 3 equiv of Ag₂O, 1 equiv of PivOH, HFIP, 100 °C, N₂ atmosphere, 24 h.

Scheme 198. Sulfur-Doped Dibenzohepta- and Dibenzooctazethrene

Reagents and conditions: (a) Pd₂(dba)₃, Na₂CO₃, SPhos, toluene/ethanol/H₂O (10:1:1), 110 °C; (b) 30% H₂O₂, acetic acid/chloroform (1:1), rt; (c) (1) Eaton’s reagent, rt, (2) pyridine/H₂O, reflux; (d) NO₂SbF₆, DCM/MeCN, rt.

Scheme 199. Synthesis of Ascididemin-Type Analogues (Deazaascididemin)

Reagents and conditions: (a) corresponding boronic acid, KF, Pd₂(dba)₃, (t-Bu)₃P, THF, 80 °C, 30 min; (b) TMPMgCl·LiCl, THF, 2 h at 0 °C, then 16 h, rt; (c)i-PrMgCl·LiCl, THF, 0 °C, 2 h.

Scheme 200. Synthesis of Amphimedine

Reagents and conditions: (a) AcOH, DMSO/HCl (conc.); (b) O₂, 1 N NaOH; (c) HBr, AcOH, 80 °C; (d) (1) Ag₂O, CeCl₃·7H₂O, MeOH/AcOH (1:1), 40 °C, (2) 6 N HCl, 90 °C; (e) (CH₂O)_n, AcOH, 60 °C, 5 h; (f) K₃[Fe(CN)₆], aq. NaOH, 0 °C.

Scheme 201. Polycyclic Heterahelicenes

Reagents and conditions: (a)^, (1) DMF, POCl₃, 90 °C, 8 h, (2) NaH₂PO₄, NaClO₂, H₂O₂, MeCN, 60 °C, 1 h; (b) 1 M NaOH; (c) 1 M HCl.

Scheme 202. Cationic Helicenes

Reagents and conditions: (a) RNH₂ (3 equiv), PhCOOH, NMP, 60 °C, 3 h; (b) RNH₂ (25 equiv), PhCOOH, NMP, 70 °C, 7 h; (c) 1,3,3-trimethyl-2-methyleneindoline, benzophenone, 80 °C, 21 h; (d) 1,3,3-trimethyl-2-methyleneindoline, (i-PrO)₃Al, benzophenone, 80 °C, 24 h; (e) i-Pr₂NEt (3.0 equiv) at 90 °C, NMP.

Scheme 203. V-Shaped Dioxaphenalene Dyes

Reagents and conditions: (a)^, (1) H₂SO₄, (2) K₂CO₃; (b) Ac₂O, DMAP.

Scheme 204. N-Arylation of 1-Amino-9-thioxanthone by Heteroaryl Iodides

Reagents and conditions: (a) 0.2 equiv of activated Cu, 2 equiv of K₂CO₃, Bu₂O, reflux, 24 h.

Scheme 205. Synthesis of Oxygen- and Nitrogen-Doped Hydrocarbons

Reagents and conditions: (a) 3,5-di-tert-butyl-2-hydroxybenzaldehyde, toluene, TFA, O₂, 100 °C, 16 h; (b) neat, 180 °C, 24 h.

Scheme 206. Double C–H Activation/Annulation of Benzamides with Aryl Alkynes

Reagents and conditions: (a) [Cp*RhCl₂]₂ (5 mol %), CF₃CO₂Ag (30 mol %), Ag₂O, Mg(OAc)₂·4H₂O, PivOH, DCE, 85 °C, under N₂, 12 h; (b) phenyliodine(III) bis(trifluoroacetate), BF₃·Et₂O, DCM, N₂, −40 °C, 2 h.

Scheme 207. Synthesis of Boronate-Based Benzo[fg]tetracene

Reagents and conditions: (a) BBr₃, Brønsted bases, 120 to 200 °C, 18 h; (b) (1) BCl₃, toluene, 0 °C to reflux, (2) AlCl₃, reflux; (c) MesMgBr, benzene, rt; (d) (1) KHMDS, toluene, rt, (2) BCl₃, 0 °C to rt, (3) AlCl₃, reflux, (4) MesMgBr, benzene, rt.

Scheme 208. Preparation of 1,9-Dibora-9a-azaphenalenyl (DBAP) Anionic Species

Reagents and conditions: (a) dichlorophenylborane, toluene, 0 °C to reflux; (b) (1) LiHMDS, toluene, 0 °C to rt, (2) dichlorophenylborane, 0 °C to reflux; (c) 18-crown-6, K, THF; (d) 208.3.

Scheme 209. Synthesis of NBN-Dibenzophenalene Derivatives

Reagents and conditions: (a) Cs₂CO₃, Pd(PPh₃)₄, toluene/EtOH; (b) BCl₃, Et₃N, o-DCB.

Scheme 210. Synthesis of a Doubly BN-Doped Dibenzoperylene Derivative

Reagents and conditions: (a) BBr₃, NaBPh₄, toluene, reflux, 18 h; (b) NBS, DCM/CHCl₃/MeCN, 0 °C, 2 h; (c) B₂pin₂, KOAc, Pd(dppf)Cl₂, 1,4-dioxane, 90 °C, 18 h; (d) Pd(PPh₃)₄, K₂CO₃, toluene/EtOH/H₂O, reflux, 18 h; (e) degassed aq. H₂SO₄ (2 M), THF, 50 °C, 5 days.

Scheme 211. DABNA and Its Carbazole-Based Analogues

Reagents and conditions: (a)^, HNPh₂ (2.2 equiv), t-BuOK (2.5 equiv), (AMPHOS)₂PdCl₂ (1.0 mol %), o-xylene, 80 °C, 2 h then 120 °C, 3 h; (b) (1) t-BuLi (1.2 equiv), t-butylbenzene, 60 °C, 2 h, (2) BBr₃ (1.2 equiv), rt, 0.5 h; EtN(i-Pr)₂ (2.0 equiv), 120 °C, 3 h.

Scheme 212. Intramolecular Borylation via Sequential B–Mes Bond Cleavage

Reagents and conditions: (a)t-BuLi and MesB(OMe)₂, THF, −78 °C; (b) (1) BBr₃, toluene, 110 °C, 24 h, (2) R–Li (2.4 equiv), THF or Et₂O, −78 °C to rt, 12 h.

Chart 20. Oxygen-Bridged Triphenylamine Skeletons

Chart 21. Metal Complexes with NBO-Doped Polycyclic Ligands

Scheme 213. Synthesis of Porous Covalent Quinazoline Networks

Reagents and conditions: (a) ZnCl₂, 300–400 °C.

Scheme 214. Synthesis of Azaullazines

Reagents and conditions: (a)p-TSA, xylene, 120 °C, 24 h.

Scheme 215. π-Extended Ullazine with a Benzoisoindole Core

Reagents and conditions: (a) for 215.2a: n-BuLi, triisopropylsilylacetylene, THF, 0 °C to rt, 3 days, 215.2b: phenyllithium, THF, rt, 3 days, 215.2c: n-BuLi, 2-bromobenzothiophene, THF, −78 °C to rt, 3 days; (b) SnCl₂, DCM, rt, 3 days.

Scheme 216. Synthetic Routes of the Ullazine Derivatives

Reagents and conditions: (a) (1) 1,4-diphenylbut-2-yne-1,4-dione, DCM, 5 min, rt, (2) DDQ, toluene, rt, 3 h; (b) hydrazine, ethanol, overnight, 80 °C; (c) (1) 1,2-naphthoquinone, DCM, TEA, rt, 5 min, (2) DDQ, toluene, rt, 3 h; (d) HOAc, toluene, 100 °C, 72 h; (e) Pd(dppf)Cl₂, Na₂CO₃, DMSO, 100 °C, 16 h; (f) PdCl₂(PPh₃)₂, PPh₃, K₂CO₃, DMF/H₂O, 90 °C, 24 h; (g) hν (254 nm), decalin, 100 °C, 2 h; (h) (1) i-Pr₂NEt, CsF, DMSO, 160 °C, 12 h, (2) DDQ, DCM, rt, 20 min; (i) Pd(AcO)₂, P(t-Bu)₂Me·HBF₄, DBU, DMA, 160 °C, 12 h.

Scheme 217. Synthesis of π-Extended Cycl[3,3,2]azines

Reagents and conditions: (a) imidazole, 120 °C, 2 h; (b) AcOH, Ac₂O, malononitrile, reflux.

Scheme 218. On-Surface Synthesis of Fused Azananographenes

Reagents and conditions: (a) Et₃N, DCM, rt, 5 min; (b) DDQ, toluene, rt, 3 h; (c) PhLi (excess), THF, rt, 3 days; (d) SnCl₂, DCM, rt, 2 h; (e) 300 °C on Au(111).

Scheme 219. π-Extended Pyrrolopyrroles with a Double-Helicene Structure

Reagents and conditions: (a)p-TsOH, AcOH, 90 °C, 3 h; (b) Pd(AcO)₂, PPh₃, Cs₂CO₃, toluene, 120 °C, 3 h; (c) FeCl₃, DCM, MeNO₂, rt, 0.5 h.

Scheme 220. Synthesis of π-Extended Aza-BODIPYs

Reagents and conditions: (a) CH₃CO₂NH₄, EtOH, reflux; (b) (1) 2 equiv of Br₂, DCM, rt, (2) 4-alkylphenylboronic acid, Pd(PPh₃)₄, Na₂CO₃, (3) Et₃N, BF₃·Et₂O; (c) TfOH, DDQ, DCM, rt.

Scheme 221. Azabuckybowl Synthesis via 1,3-Dipolar Cycloaddition of Corannulene

Reagents and conditions: (a)^,i-Pr₂NEt, DMSO, 120–140 °C, 1–20 h; (b) DDQ (1.8–4.2 equiv), DCM, rt, 10 min–14 h; (c) Pd(OAc)₂, t-Bu₂PMe·HBF₄, DBU, DMA, 150 °C, 24 h.

Scheme 222. Aza-Annulative π-Extension Reaction of Corannulene

Reagents and conditions: (a) (1) AgPF₆, 1,2-DCE, 80 °C, 17 h, (2) p-chloranil, rt, 3 h.

Scheme 223. Transition-Metal-Free, One-Pot Thienannulation of Corannulene

Reagents and conditions: (a) (1) Tf₂O, 1,2-DCE, −30 °C, 20 min, then rt, 1 h, (2) microwave, 90 °C, 12 h, (3) Et₃N, rt, 20 min, then 50 °C, 5 h.

Scheme 224. Thienannulation of Arylethynyl-Substituted Corannulenes with Elemental Sulfur

Reagents and conditions: (a) S₈ (0.5 equiv), 140 °C, 24 h; (b) S₈ (5 equiv), DMF, 140 °C, 48 h.

Scheme 225. Synthesis of Diindole-Fused Corannulene Imide by Reductive Ring Closure

Reagents and conditions: (a) PPh₃, dry o-dichlorobenzene, 180 °C, 36 h.

Scheme 226. π-Extension of Corannulene via Photocyclization

Reagents and conditions: (a) (1) n-BuLi, THF, 0 °C, 30 min, (2) 2-thiophenecarboxaldehyde, rt, 2 h; (b) I₂, propylene oxide, medium-pressure Hg lamp (125 W), toluene; (c) Pd₂(dba)₃, rac-BINAP, t-BuONa, toluene, 110 °C, 12 h.

Scheme 227. Synthesis of Doubly Fused Corannulene Tetrasulfone

Reagents and conditions: (a) (1) benzene-1,2-dithiol, t-BuOK, DMF, rt, 1 h, (2) 60 °C, 21 h; (b) m-CPBA, DCM, rt, 48 h.

Scheme 228. Synthesis of Azaindenocorannulenes

Reagents and conditions: (a) [i-Pr₃Si]⁺[CB₁₁H₆Cl₆]⁻, (MeS)₂SiMe₂, chlorobenzene, microwave (225 W), 110 °C, 2 h; (b) Pd(PCy₃)₂Cl₂, DBU, DMA, microwave (300 W), 160 °C, 0.5 h; (c) 2-chloropyridine-3-boronic acid (4 equiv), Pd(PPh₃)₄, K₂CO₃, THF/H₂O (9/1), 100 °C, 1.5 h; (d) 2-chloropyridine-3-boronic acid (8 equiv), Pd(PPh₃)₄, K₂CO₃, THF/H₂O (9/1), 100 °C, 1.5 h; (e) 2-chlorophenylboronic acid, Pd(PPh₃)₄, K₂CO₃, THF/H₂O (9/1), 100 °C, 1.5 h; (f) Pd(PCy₃)₂Cl₂, DBU, DMA, 160–180 °C, 6–7 h.

Scheme 229. Preparation of 4-Fold Fused [7]Circulene Derivatives Bearing Four or Two Thieno Fusions

Reagents and conditions: (a) NaCl, AlCl₃, 150 °C, 0.5 h; (b) CBr₄, PPh₃, toluene, 80 °C, 24 h; (c) (3-bromothiophen-2-yl)boronic acid pinacol ester, Pd(PPh₃)₄, K₂CO₃, THF/H₂O (10/1), reflux, 24 h; (d) Pd(PPh₃)₄, Cs₂CO₃, toluene, reflux, 24 h; (e) 2-bromophenylboronic acid, Pd(PPh₃)₄, K₂CO₃, THF/H₂O (10/1), reflux, 24 h.

Scheme 230. Attempted Synthesis of 5-Azadibenzo[a,g]corannulene by Solution-Phase Synthesis and Flash Vacuum Pyrolysis

Reagents and conditions: (a) Pd(PCy₃)₂Cl₂, DBU, DMA, 150 °C, 3 days; (b) FVP, 1000 °C; (c) silica gel, dry DCM, 24 h.

Scheme 231. Gram-Scale, Four-Step Synthesis of B₂N₂ Corannulene

Reagents and conditions: (a) phenylboronic acid, Pd(PPh₃)₄, K₂CO₃, THF/H₂O (1:1), reflux, 3 days; (b) Zn, acetic acid, 40 °C, 22 h; (c) 2,2-diphenylacetic acid, 180 °C, 62 h; (d) BBr₃, o-dichlorobenzene, reflux, 16 h.

Scheme 232. Regioselective Five-Fold C–H Functionalization of Azabuckybowl

Reagents and conditions: (a) (a) i-Pr₂NEt, DMSO, 100 °C, 9 h; (b) DDQ, DCM, rt, 5 min; (c) Pd(OAc)₂, t-Bu₂PMe·HBF₄, DBU, DMA, 140 °C, 18 h; (d) B₂pin₂, [Ir(OMe)(cod)]₂, 4,4′-di-t-butyl-2,2′-bipyridine, t-BuOK, THF, 85 °C, 10 days; (e) 1,2,3-trialkoxy-5-bromobenzene, Pd₂(dba)₃·CHCl₃, SPhos, Cs₂CO₃, toluene/H₂O (2/1), 80–85 °C, 3–5 days.

Scheme 233. Chemical Reduction of an Azapentabenzocorannulene Derivative

Reagents and conditions: (a) Na (8 equiv), 18-crown-6, THF, Ar, 25 °C, 48 h; (b) Cs (2 equiv), 18-crown-6, THF, Ar, 25 °C, 5 min; (c) Cs (5 equiv), 18-crown-6, THF, argon, 25 °C, 30 min.

Scheme 234. Bis(azapentabenzocorannulene)s

Reagents and conditions: (a) Pd(OAc)₂ (0.2 equiv), PCy₃·HBF₄ (0.4 equiv), K₂CO₃ (8 equiv), DMA, 130 °C, 29 h; (b) 3,6-dibromo-9H-carbazole, Pd(PPh₃)₄, Cs₂CO₃, THF/H₂O (4/1), reflux, 4 h; (c) 3,6-diiodophenanthrene, Pd(PPh₃)₄, Cs₂CO₃, dioxane/H₂O (20/3), 80 °C, 1 h.

Scheme 235. Synthesis and Reversible Dimerization of Azabuckybowl Derivatives

Reagents and conditions: (a) Pd(OAc)₂ (2 equiv), PCy₃·HBF₄ (4 equiv), K₂CO₃ (8 equiv), DMA, 130 °C, 32 h; (b) BAHA (1 equiv); (c) crystallization or cooling in solution; (d) heating in solution; (e) MeOH, DCM/toluene/Et₂O (3:2:1) (for crystallization) or CDCl₃ (for NMR).

Scheme 236. Syntheses of Unsubstituted Trichalcogenasumanenes from Triphenylene-Based Precursors

Reagents and conditions: (a)m-CPBA, TfOH, DCM, 0 °C to rt, 12 h; (b) AcSK, CuCl₂, DMSO, 110 °C, 48 h; (c) S₈ powder, Cs₂CO₃, DMSO, 140 °C, 12 h; (d) S₈ powder, Cs₂CO₃, DMSO, 80 °C, 12 h; (e) Cu, tetralin, 200 °C, 1–2 h; (f) Se powder, t-BuOK, DMSO, 70 °C, 24 h; (g) Te powder, 2-picoline, DMSO, 125 °C, 12 h; (h) (1) HCl, NaNO₂, H₂O, 0 °C, (2) KSCN, FeCl₃, 0 °C, then rt, 1 h; (i) Na₂S·9H₂O, EtOH/H₂O (2/1), reflux, overnight; (j) PdCl₂ (90 mol %), DMSO, 120 °C, 24 h.

Scheme 237. Six-Fold Functionalized Trithiasumanenes

Reagents and conditions: (a) Br₂, Fe, nitrobenzene, 80 °C, 2 days; (b) RSNa, dry 1,3-dimethyl-2-imidazolidinone, rt, 8 h; (c) BBr₃, DCM, 0 °C to rt, then H₂O; (d) R′Br, K₂CO₃, DMF, 75 °C.

Scheme 238. Ring-Modified Trichalcogenasumanenes

Reagents and conditions: (a)^,n-BuLi (2.2 equiv), TMEDA, hexane, −30, 60 °C or reflux, 30 min–3 h; (b) (1) PhPCl₂, THF, −78 °C to rt, 3–4 h, (2) S powder, rt, 12.5–14 h; (c) THF, −78 °C to rt, then reflux, 12 h; (d) 30% aq. H₂O₂, DCM/AcOH (1/2), 60 °C, 24 h.

Scheme 239. Gram-Scale, One-Pot Synthesis of a Tritellurasumanene Derivative and Its Subsequent Halogenation

Reagents and conditions: (a) (1) n-BuLi, TMEDA, hexane, 60 °C, 3 h, (2) Te powder, ultrasound, rt, 12 h; (b) Br₂, DCM, rt, 15 min; (c) I₂ (yield not given); (d) FeCl₃, DCM, MeNO₂, rt, 2 h.

Scheme 240. Synthesis and Reactivity of Trichalcogenasumanene Derivatives Bearing Two Different Chalcogens

Reagents and conditions: (a)n-BuLi (4, 5, or 10 equiv), TMEDA, hexane, 60 °C, 3 h; (b) Se powder (10 equiv), THF, −78 °C to rt, 8 h; (c) Cu nanopowder, 215 °C, 160 min; (d) Te powder (10 equiv), ultrasound, rt, 12 h; (e) oxone, THF/H₂O (4/1), rt, 12 h; (f) 30% aq. H₂O₂, DCM/AcOH (5/1), 24 h; (g) Br₂, DCM, rt, 15 min.

Scheme 241. Trithiasumanene and Triselenasumanene Derivatives via Copper-Catalyzed Dechalcogenization

Reagents and conditions: (a) CuI (40 mol %), 1,10-phenanthroline (80 mol %), K₂CO₃ (6 equiv), DMSO/H₂O (20:1), air, 160 °C; (b) CuI (20 mol %), 1,10-phenanthroline (40 mol %), K₂CO₃ (3 equiv), DMSO/H₂O (20:1), air, 160 °C.

Scheme 242. [6]Heteracirculenoids Bearing Chalcogenole and Pyridine Rings

Reagents and conditions: (a)t-BuONO, DCM, rt, 4 h; (b) Zn, AcOH/EtOH, 0 °C, 10 min, then rt, 3 h; (c) TFA, 120 °C, 12 h.

Scheme 243. Oxidative Ring Opening of Trichalcogenasumanenes

Reagents and conditions: (a) oxone, THF/H₂O (4:1), rt, 2 h; (b) (1) NaOH, EtOH/H₂O (10:1), reflux, 2 h, (2) aq. HCl (3 N); (c) Ac₂O, reflux; (d) o-phenylenediamine, DCC, THF, reflux, 8 h; (e)t-BuOOH (6 equiv), DCM, 40 °C, 5 h; (f) (1) p-toluidine, DCC, THF, reflux, 12 h.

Scheme 244. Synthesis and Reactivity of Trichalcogenasumanene-Derived ortho-Quinone

Reagents and conditions: (a) FeCl₃, DCM, MeNO₂, rt, 2 h; (b) 1,2-diphenylethane-1,2-diamine, AcOH, reflux, 12 h; (c) 1,8-naphthalenediamine, AcOH, reflux, 4 h.

Chart 22. Tetrathiafulvalene-Fused Compounds with a D₁–A–D₂ or D–A Structure

Scheme 245. Dativizations of Enantiopure Tris(methylthio)-Substituted Triazasumanene

Reagents and conditions: (a) RB(OH)₂, Pd₂(dba)₃, tri(2-furyl)phosphine, copper(I) thiophene-2-carboxylate (CuTC), THF, 50 °C, 12 h; (b) Et₂MeSiH or poly(methylhydrosiloxane) (PMHS), Pd₂(dba)₃, tri(2-furyl)phosphine, CuTC, THF, 50 °C, 30 min; (c) MeOH/H₂O, pH = 2.01; (d) DCl, CD₃OD/D₂O.

Scheme 246. Attempted Oxidative and Reductive Fold-In Syntheses of Strained Triazasumanene Derivatives

Reagents and conditions: (a) FeCl₃, AgOTf, DCM/MeNO₂ (10:1), rt, 24 h; (b) NBS, DMF, 0 °C, 6 h; (c) MeI, NaH, DMF, rt, 3 h; (d) Pd[P(t-Bu)₃]₂, K₃PO₄, toluene, 110 °C, 24 h.

Chart 23. Aza[n]helicenes via Photochemical Cyclization

Scheme 247. Synthesis of Tetraaza[8]circulene Derivatives via S_NAr Reaction

Reagents and conditions: (a)p-toluidine, KHMDS, 1,4-dioxane/toluene, 85 °C, 24 h.

Scheme 248. Syntheses of Tetrabenzotetraaza[8]circulenes

Reagents and conditions: (a) DDQ, TfOH, DCM, rt, 10 min–6 h; (b) 1-iodooctane, NaH, DMSO, 50 °C, 38 h; (c) m-CPBA, CHCl₃, reflux, 3 h; (d) aniline or 4-tert-butylaniline, KHMDS, dioxane, 90 °C, 24 h; (e) diphenylmethane, KHMDS, dioxane, 90 °C, 24 h; (f) BAHA, DCM, rt, 30 min; (g) SPhos Pd G2, K₃PO₄, THF/H₂O, 60 °C, 12 h; (h) DDQ, Sc(OTf)₃, toluene, darkness, reflux, 2–5 h.

Chart 24. Structures of Tetraaza[8]circulene Derivatives

Scheme 249. Tetrathia[8]circulenes and Their Aza-, Sila-, and Germa-Substituted Derivatives

Reagents and conditions: (a) NIS, CuI, DMF, 80 °C, 3 h; (b) Pd(PPh₃)₂Cl₂, CuI, Et₃N, 60 °C, 3 h; (c) DBU, NMP, reflux, 12 h; (d) CuSO₄·5H₂O, K₂CO₃, N,N′-dimethylethylenediamine, toluene, 80 °C, 20 h; (e) POCl₃, toluene, 120 °C, 2 h; (f) R²SiH₂, Pd(t-Bu₃P)₂, Et₃N, THF, rt, 48 h; (g) Et₂GeH₂, Pd(t-Bu₃P)₂, i-Pr₂NEt, THF, rt, 18 h; (h) [RhCl(cod)]₂, dppf, toluene, 140 °C, 24 h; (i) [RhCl(cod)]₂, (C₆F₅)₂PCH₂CH₂P(C₆F₅)₂, toluene, 140 °C, 20 h.

Scheme 250. Synthesis of Diazadithia- and Diazadiselena[8]circulenes under Mild Conditions

Reagents and conditions: (a) (1) n-BuLi, THF, −78 °C, (2) H₂O, −78 °C, 1 h, then rt, 2 h; (b) (1) n-BuLi, THF, −78 °C, (2) TMSCl, −78 °C, 1 h, then rt, 2 h; (c) n-BuLi, THF, −78 °C, 3 h, (2) S powder or Se powder, −78 °C, 2 h, then rt, overnight; (d) Cu powder, 250 °C.

Scheme 251. Synthesis of a Planar Diazaoxathia[8]circulene Skeleton by Compression of a Nonplanar [7]Helicene Precursor

Reagents and conditions: (a) (1) NaH, DMF, 0–25 °C, 40–45 min, (2) dimethylthiocarbamoyl chloride, 85 °C, 2 h; (b) 300 °C, 25 min; (c) t-BuOK, O₂, DMSO, 25 °C, 1 h; (d) chloranil, BF₃·OEt₂, MeCN/DCM, 25 °C, 40–45 min; (e) m-CPBA, THF/DCM, 25 °C, 30–45 min; (f) n-Bu₄NI, BCl₃, MeCN/DCM, 25 °C, 1 h.

Scheme 252. Oxidative and Dehydrative Cyclization Reactions between Pyrrole and Indole Units

Reagents and conditions: (a) (1) PIFA (2.5 equiv), DCM, −78 °C, 30 min, (2) rt, 1 h; (b) DDQ (5 equiv), Sc(OTf)₃ (5 equiv), toluene, reflux, 2–3 h; (c) PIFA (3.0–3.5 equiv), DCM, −78 °C, 3 h, (2) rt, 45 min; (d) BBr₃, DCM, rt, 12 h.

Scheme 253. Iterative Deprotonation–Coupling Approach toward Thiophene-Based Double Helices^,

For all the racemates, the absolute configurations of the chiral axes of depicted enantiomers are shown to facilitate discussion. Reagents and conditions: (a)n-BuLi (2.1 equiv), THF, −78 °C, 2 h, then 60 °C, 2 h; (b) CuBr₂, Et₂O, −78 °C, 1 h, then rt, overnight; (c) ZnCl₂, −78 °C, then rt; (d) 253.6, Pd(PPh₃)₄, Et₂O, 120 °C, 48 h; (d) CuCl₂, Et₂O, −78 °C, 2 h, then rt, 24 h.

Scheme 254. Arylation and Attempted Vertical Extension of a Thiophene-Based Double Helix

Reagents and conditions: (a)n-BuLi, THF, −78 °C, then 60 °C, 2 h; (b) ZnCl₂, −78 °C, then rt; (c) 3-bromothiophene, Pd(PPh₃)₄, THF, 120 °C, 48 h; (d) C₂Br₂Cl₄, −78 °C, then rt, overnight; (e) phenylboronic acid, Cs₂CO₃, THF/H₂O (50:1), 100 °C; (f) 253.6, Pd(PPh₃)₄, THF, 120 °C; (g) 254.7, Pd(PPh₃)₄, THF, 120 °C.

Scheme 255. Synthesis of Sulflower and Related Systems

Reagents and conditions: (a)n-BuLi, Et₂O, −78 °C, then 60 °C, 2 h; (b) (PhSO₂)₂S, −78 °C, then rt, overnight; (c) TFA, DCM, rt, monitor by TLC until complete reaction; (d) LDA (4.1 or 2.1 equiv), THF, 0 °C, 2 h; (e) TFA, DCM, rt, then aq. NaHCO₃ right after addition of TFA.

Scheme 256. Combined In-Solution/On-Surface Approach toward a π-Extended Diaza[8]circulene Derivative^,

Reagents and conditions: (a)i-Pr₂NEt, DMSO, 140 °C, 6 h–18 h; (b) DDQ, DCM, rt, 10–1 h; (e) >430 °C on Au(111). Level of theory: B3LYP/6-31G(d).

Scheme 257. Syntheses of Derivatives of Diazatrioxa[9]circulene and Diazatetraoxa[10]circulene

Reagents and conditions: (a) DDQ, DCM, rt; (b) H₂SO₄, AcOH, rt, 5–16 h; (c) chloranil, BF₃·Et₂O, DCM, rt, 45 min.

Scheme 258. Synthesis of Carbazole-Based Macrocyclic Tetraradicaloid and Hexaradicaloid

Reagents and conditions: (a) Pd₂(dba)₃, t-Bu₃P·HBF₄, NaHCO₃, THF/H₂O, 85 °C, 72 h; (b) (1) MesMgBr, THF, rt, 24 h, (2) BF₃·OEt₂, DCM; (c) DDQ, DCM, rt, 10–30 min.

Scheme 259. Dibenzothiophene–Phenanthrene-Based Macrocycles

Reagents and conditions: (a) Na₂S·9H₂O, CuI, 1,10-phenanthroline, DMF, 140 °C, N₂, 16 h; (b) FeCl₃, DCM/MeNO₂, bubbling with N₂, 0 °C, 10 min; (c) Pd₂(dba)₃, t-Bu₃P·HBF₄, NaHCO₃, THF/H₂O, 80 °C, 2 days; (d) premixed [MeOCH₂PPh₃]⁺Cl^– and t-BuOK, THF, rt, 2 h; (e) Bi(OTf)₃, dry 1,2-DCE, rt, 3 h; (f) (1) MesMgBr, THF, rt, overnight, (2) BF₃·OEt₂, DCM, 3 h; (g) DDQ, DCM, rt, 6 h.

Scheme 260. Phenazine-Fused Porous Conjugated Frameworks

Reagents and conditions: (a) dioxane/AcOH (1:4), 135 °C, 7 days; (b) TfOH, 175 °C.

Chart 25. Acenaphthylene-Based Quinoxalines

Chart 26. Pyracylene-Based Quinoxalines

Scheme 261. Synthesis of N-Doped Rubicenes

Reagents and conditions: (a) pyridine, 90 °C, 16–48 h; (b) Sc(OTf)₃, 1,2-DCE, 25 °C, 24 h; (c) (1) 1,3-butadiene, Ru₃(CO)₁₂, t-Bu₂PMe·HBF₄, t-BuOK, i-PrOH, toluene with or without DMA, 140 °C, 48 h, (2) TsOH, toluene, 90 °C, 16 h.

Scheme 262. Miscellaneous Acenaphthylenes Hetero[a]fused with Nitrogen Heterocycles

Reagents and conditions: (a) MesSO₃NH₂, DCM, 1 h; (b) acenaphthoquinone, NaOAc, EtOH, reflux, 1 h; (c)hν (254 nm, 6 × 8 W), 48–72 h; (d) R′C≡CH, CuI (10 mol %), 1,10-phenanthroline (20 mol %), Cs₂CO₃ (1 equiv), dioxane, 100 °C, 26–32 h.

Scheme 263. Formation of an Acenaphtho[1,2-b]benzo[g]indole Skeleton via Cascade Reaction

Reagents and conditions: (a) Pd₂(dba)₃, CuI, PPh₃, K₂CO₃, DMF, argon, 60–75 °C, 8–10 h.

Scheme 264. Five-Membered Ring Closures Involving a Thiophene Ring

Reagents and conditions: (a) Pd(OAc)₂, t-Bu₂PMe·HBF₄, K₂CO₃, DMA, 100 °C, 20 h; (b) (1) 3,5-di-t-butylphenylacetylene, n-BuLi (premixed at −78 °C for 1 h), then rt for 1 h, THF, rt, overnight, (2) SnCl₂·H₂O, 10% aq. HCl, 50 °C, 2 h; (c)p-chloranil (1.5 equiv), DCM/TfOH (100/1), rt, 6 h.

Scheme 265. Thiophene-Fused Rubicene-Based Conjugated Polymers^,

Reagents and conditions: (a) Pd(OAc)₂ K₂CO₃, n-Bu₄NHSO₄, MeCN, reflux, 24 h; (b) NBS, THF, 0–35 °C, 12 h; (c) 265.5, Pd(PPh₃)₄, K₂CO₃, toluene, 110 °C, microwave, 12 h; (d) 265.6, Pd(PPh₃)₂Cl₂, toluene, 110 °C, microwave, 12 h; (e) FeCl₃, DCM/MeNO₃, argon, rt, overnight Only one out of three possible isomeric constitutions of the repeat unit is shown for polymers 265.7a and 265.8a–c. Calculation was performed on the repeat unit of the structures shown (B3LYP/6-31G**). Alternative regioisomeric repeat units were also calculated.

Scheme 266. Thieno[j]fluoranthenes

Reagents and conditions: (a) KHMDS (3 equiv), cis-1,2-cyclohexanediol (20 mol %), diglyme, reflux, 24 h.

Scheme 267. Hetero[e]fused Acenaphthylenes from C–H Annulation Reactions^,

Reagents and conditions: (a) [RhCp*Cl₂]₂ (20 mol %), AgSbF₆ (40 mol %), Cu(OAc)₂ (4.0 equiv), dioxane, 130 °C, 3 h; (b) (1) Tf₂O, 1,2-DCE, −30 °C, 20 min, then rt, 1 h, (2) microwave, 90 °C, 12 h, (3) Et₃N, rt, 20 min, then 50 °C, 5 h. The sequence of formation of the five new C–C bonds determined by DFT calculation for 267.3a is shown in red.

Scheme 268. Hetero[e]fused Acenaphthylenes from C–H Annulation Reactions

Reagents and conditions: (a) Pd(PPh₃)₄ (5 mol %), t-BuOLi (2 equiv), K₂CO₃ (1 equiv), KOAc (1 equiv), dioxane, N₂, 100 °C, 24 h; (b) FeCl₃, DCM/MeNO₂, 0 °C; (c) FeCl₃, DCM/MeNO₂, rt; (d) FeCl₃, DCM/MeNO₂, 0 °C, 15 min, then rt, 2.5 h; (e) (1) DDQ, DCM, 0 °C, 10 min, (2) TfOH, 10 min.

Scheme 269. Synthesis of Heterocycle-Fused π-Extended Truxenes

Reagents and conditions: (a) B₂pin₂, [Ir(OMe)(cod)]₂, 4,4′-di-t-butyl-2,2′-bipyridine, t-BuOK, THF, 80 °C, 24 h; (b) 3-bromothiophene-2-carboxaldehyde, Pd₂(dba)₃ (10 mol %), t-Bu₂PMe·HBF₄ (17 mol %), K₂CO₃, THF/H₂O (4:1), 80 °C, 16 h; (c) t-BuOK, THF, 60 °C, 16 h.

Scheme 270. Synthesis of a Contorted Polyarene in a Cyclopentannulation–Cyclodehydrogenation Sequence^,

Reagents and conditions: (a) Pd₂(dba)₃, tri(o-tolyl)phosphine, KOAc, LiCl, DMF/toluene, 130 °C; (b) FeCl₃, DCM/MeNO₂. Level of theory: B3LYP/6-311G(d,p).

Scheme 271. Lactam-Fused Carbazole Derivatives^,

Reagents and conditions: (a) diethyl malonate (3 equiv), diphenyl ether, 250–260 °C, 7 h; (b) NaOH, ethylene glycol, 180 °C, 3 h; (c) P₂O₅, MsOH, 150 °C, 20 min; (d) DMF, reflux, 2 h; (e) bromobenzene, reflux, 3 h; (f) AcOH, reflux, air, 30–40 h. The chains of atoms in 271.1 that originate from the first and second reacting diethyl malonate molecules are shown in blue and green, respectively.

Scheme 272. Synthesis of a Diindole-Fused Azapentacenone

Reagents and conditions: (a) CuI, K₂CO₃, 18-crown-6, o-dichlorobenzene, 180 °C, N₂, 24 h; (b) (1) NaOH, MeOH, reflux, 10 h, then aq. HCl; (c) DMF (cat.), SOCl₂, reflux, 1 h; (d) AlCl₃, DCM, rt, 12 h.

Scheme 273. Fused Bicarbazoles

Reagents and conditions: (a) [n-Bu₄N][MnO₄], pyridine, 70 °C, 24 h; (b) Ni(cod)₂ (150 mol %), cod (150 mol %), 2,2′-bipyridyl (150 mol %), THF, 55 °C, 24 h; (c) naphthalene, Li, THF, 0 °C, 1 h; (d) (1) DDQ, DCM, 0 °C, then rt, 2 h, (2) N₂H₄·H₂O, 0 °C; (e) NOSbF₆ (1.0 equiv), DCM/MeCN, rt, 1 h; (f) NOSbF₆ (2.1 equiv), DCM/MeCN, rt, 30 min.

Scheme 274. Carbonyl-Free Azafluoranthene Derivatives

Reagents and conditions: (a) EtOH, reflux, 1 h; (b) N₂H₄·H₂O, EtOH, reflux, 8 h; (c) Cu(OTf)₂ (100 mol %), MeCN, 80 °C, 12 h; (d) Cu(OTf)₂ (10 mol %), Selectfluor (1.0 equiv), MeCN, 80 °C, 12 h; (e)ortho-phenylenediamine (2.5 equiv), Na₂CO₃ (3 equiv), Cu(OAc)₂ (0.1 equiv), i-PrOH/ethylene glycol (9:1), argon, reflux, 16 h; (f) TsOH·H₂O (0.1 equiv), EtOH, reflux.

Scheme 275. Synthesis of a Fused Benzimidazoisoquinoline–Quinoxaline

Reagents and conditions: (a) Cs₂CO₃, CuI, DMF, microwave, 150 °C, 10 min.

Scheme 276. Three-Component Cascade Condensation

Reagents and conditions: (a) 10% HClO₄, MeOH, microwave, 100 °C, 10 min.

Scheme 277. MeOTf-Induced Cyclization of N-(2-Cyanophenyl)carbazole

Reagents and conditions: (a) MeOTf (1.2 equiv), 1,2-DCE, air, 90 °C, 24 h.

Scheme 278. Base-Promoted Cyclization toward an Alpkinidine Analogue

Reagents and conditions: (a) NaHMDS, THF, −95 °C, 10 min, then rt, 4 h; (b) (1) NaOEt, EtOH, rt, 2 h, (2) allyl bromide, 6 h.

Scheme 279. Synthesis of Triptycene-Capped Indigo Derivatives

Reagents and conditions: (a) Cl₃CCH(OH)₂, Na₂SO₄, H₂O, 50 °C, then conc. HCl, 5 min, (2) aq. NH₂OH·HCl, 80 °C, 20 h; (b) MsOH, 50 °C, 4 h; (c) (1) PCl₅, toluene, 100 °C, 4 h, (2) PhSH, 50 °C, 16 h; (d) 2-thiopheneacetyl chloride, o-xylene, 155 °C, 48 h.

Scheme 280. Preparation of Thiadiazolo-Fused Triazafluoranthenones

Reagents and conditions: (a) S₄N₄, DMF, 153 °C, 7 h; (b) m-terphenyl, 270 °C, 3 h.

Scheme 281. π-Extended Heterocycle-Fused Pyracylenes

Reagents and conditions: (a)p-chloranil (1.0 equiv), DCM/TfOH (100/1), 0 °C, 10 min; (b) p-chloranil (2.0 equiv), DCM/TfOH (100:1), 0 °C, 10 min; (c) PhNH₂, PdCl₂, Et₃N, DMSO, 90 °C, 8 h.

Chart 27. Edge-Fused Organosulfur Acenes

Scheme 282. Thiophene- and Phosphole-Fused Polyarene

Reagents and conditions: (a) Cp₂ZrCl₂, THF, −78 °C, then n-BuLi, overnight; (b) (1) CuI, 0 °C, 20 min, (2) PhPCl₂, −78 °C, 15 h; (c) S₈, DCM, rt, 5 h; (d) I₂, propylene oxide, toluene, hν (mercury vapor lamp), 20 h; (e) FeCl₃, DCM.

Scheme 283. Synthesis of a Phenanthrodithiophene Derivative

Reagents and conditions: (a) NaIO₄, THF/H₂O, rt, 12 h; (b) (1) TMEDA, THF, −80 °C, 30 min, (2) n-BuLi, THF, 30 min, (3) TBDMSCl, 20 min, then rt, 12 h; (c) FeCl₃, toluene/MeNO₂, rt,.

Scheme 284. Synthesis of a Sulfur-Hybridized Pyracylene Derivative and an Unexpected Aryl Shift during Oxidative Cyclization^,

Reagents and conditions: (a) FeCl₃, DCM/MeNO₂, 5 min; (b) phenylboronic acid, K₂CO₃, Pd(PPh₃)₄, THF/H₂O, N₂, dark, 70 °C, overnight. Two corresponding carbon atoms (A and B) of compounds 284.4 and 284.5 are labeled in blue for a better understanding.

Scheme 285. Palladium-Catalyzed Diarylation with Diaryliodonium Salts

Reagents and conditions: (a) Pd(OAc)₂ (10 mol %), DMF, 100 °C, 24 h.

Scheme 286. Pentannulated Carbazoles via Palladium-Catalyzed Direct Arylation

Reagents and conditions: (a)⁻ Pd(OAc)₂, PPh₃, [BnNEt₃]Cl, K₂CO₃, DMA, reflux, 6 h; (b) NBS, DMF, rt, 12 h; (c) diphenylamine, Pd(dba)₂, t-Bu₃P, t-BuONa, xylene, reflux, 12 h; (d) (NHC)Pd(allyl)Cl (5 mol %), K₂CO₃ (2 equiv), DMA, argon, 130 °C, 4–6 h; (e) Fe powder, AcOH, 60 °C, argon, 2 h; (f) Pd(OAc)₂, PPh₃, t-BuONa, toluene, 90 °C, 24 h.

Scheme 287. Stepwise Cyclization Approach toward Highly Fused Acridones

Reagents and conditions: (a) NaOH, EtOH/H₂O, reflux, 3 h; (b) polyphosphoric acid, 180 °C, 4 h; (c) BH₃·THF, THF, reflux, 4 h; (d) Pd(OAc)₂, PCy₃·HBF₄, K₂CO₃, DMA, 170 °C, 48 h; (e) Na₂Cr₂O₇, AcOH, reflux, 1 h; (f) Br₂, DCM, rt, 48 h; (g) Pd(OAc)₂, PCy₃·HBF₄, K₂CO₃, DMA, 130 °C, 24 h; (h) DDQ, DCM/dioxane/H₂O, 0 °C to rt, 16 h.

Scheme 288. Pentannulated Carbazoles via Palladium-Catalyzed Oxidative Cyclization

Reagents and conditions: (a) palladium(II) pivalate (10 mol %), Ag₂O (1.2 equiv), CuO (1.2 equiv), pivalic acid, O₂ (1 atm), 130 °C, 24 h; (b) Ag₂O (1 equiv), toluene/cumene/AcOH, air, 60 °C, 2 h; (c) Pd(OAc)₂ (10 mol %), Ag₂O (1.2 equiv), CuO (1.2 equiv), pivalic acid, air, 130 °C, 3 days; (d) palladium(II) trifluoroacetate (30 mol %), AgOAc (6.0 equiv), pivalic acid, 160 °C, 48 h.

Scheme 289. Formation of [5,5,6] Fusion via Ullmann-Type Reaction

Reagents and conditions: (a) Cs₂CO₃, CuI, DMF, microwave, 120 °C, 10 min.

Chart 28. Substituted Indolocarbazoles

Chart 29. Covalently Linked Bis(indolocarbazole)s

Scheme 290. π-Extended Imidazole- and 1,3-Azaphosphole-Fused Indolizine Derivatives

Reagents and conditions: (a) (HONH₃)₂SO₄, NaOAc, EtOH, rt, 16 h; (b) Zn, AcOH, rt, 10 min; (c) 1-naphthylacetyl chloride, Et₃N, DCM, 0 °C, then rt, 16 h; (d) Tf₂O, 2-methoxypyridine; DCM, 50 °C, 16 h; (e) Pd₂(dba)₃ (cat.) t-Bu₃P·HBF₄ (cat.), K₂CO₃, DMF, 110 °C, 16 h; (f)n-BuLi, TMEDA, THF, 0 °C, 1 h; (g) PhPCl₂, 0 °C, 10 min, then rt, 30 min; (h) aq. H₂O₂ (30%), 30 min; (i) S₈, 30 min.

Scheme 291. Dibenzannulated Derivatives of Triazino[2,1,6-cd]pyrrolizine

Reagents and conditions: (a)t-BuOK (1 equiv), DMF, 0 °C, 1 h; (b) neat, N₂, 230 °C, 3 h; (c) [Rh(cod)Cl]₂ (5 mol %), P(Oi-Pr)₃ (0.1 equiv), i-Pr₃SiH (4 equiv), ethylcyclohexane, reflux, 15 h; (d) IrCl₃, dry ethylene glycol, N₂, reflux, 24 h; (e) EtOH/AcOH (1:1), reflux, 24 h; (f) acetylacetone, pyridine, reflux, 24 h; (g) K₂PtCl₄, 2-ethoxyethanol/H₂O (3:1), N₂, 80 °C, 24 h.

Scheme 292. Three-Component Synthesis of Fused Cycloheptatrienes

Reagents and conditions: (a) Pd(OAc)₂ (5 mol %), PCy₃ (15 mol %), Cs₂CO₃, 1,4-dioxane, 130 °C, 18 h.

Scheme 293. Total Synthesis of Radermachol

Reagents and conditions: (a) 1,3-indanedione, CsF, MeCN, 75–80 °C, 1.5 h; (b) 3-methylcrotonoyl chloride, AlCl₃, 55 °C, 2 h; (c) Me₃SiI, CDCl₃, 25 °C, 27 h; (d) TsOH, benzene, reflux, 5 h.

Scheme 294. Syntheses of [de] and [kl]Fused Dibenzoazepines via Palladium-Catalyzed Annulation

Reagents and conditions: (a)t-BuONa, Pd(OAc)₂ (3 mol %), Pd₂(dba)₃ (3 mol %), PCy₃ (7 mol %), t-Bu₃P (7 mol %), dry toluene, 90 °C, 10 h; (b) Pd(OAc)₂ (10 mol %), PPh₃ (20 mol %), norbornene (1 equiv), Cs₂CO₃ (4 equiv), toluene, 95 °C, 6 h; (c) PdCl(C₃H₅)(dppb) (2 mol %), KOAc (2 equiv), DMA, 150 °C, 72 h.

Scheme 295. [de]Fused Dibenzoazepines and Analogues via Direct Cyclization

Reagents and conditions: (a) AuCl(PPh₃) (10 mol %), AgSbF₆ (10 mol %), 1,2-DCE, 80 °C, 24 h; (b) AuCl[P(C₆F₅)₃] (10 mol %), AgOTf (10 mol %), 1,2-DCE, rt, 3 h; (c) Cs₂CO₃, CuI, DMF, microwave, 150 °C, 10 min; (d) AcCl (1.2 equiv), Et₃N (2.0 equiv), DCM, rt, 4 h; (e) polyphosphoric acid, POCl₃ (10 equiv) 120 °C, 3 h.

Scheme 296. peri-Naphtho-Fused Azepine Derivatives via Heptannulation

Reagents and conditions: (a)hν (254 nm, 2 × 8 W), DCM, rt; (b) Pd₂(dba)₃·CHCl₃, BrettPhos, t-BuONa, toluene, 80 °C, 9 h; (c) anisole, TFA, toluene, 70 °C, 4 h.

Scheme 297. Fused Diazaheptalene via Copper-Assisted Oxidative Cyclodimerization

Reagents and conditions: (a) (1) DDQ, THF, 1 h, (2) Cu(OAc)₂, overnight.

Scheme 298. Synthesis of Indole-Fused Dibenzoxazepine via Radical Cyclization

Reagents and conditions: (a) toluene, reflux, 8 h; (b) AIBN (2.2 equiv), Bu₃SnH (0.5 equiv), toluene, 80 °C, 7 h; (c) AIBN (1.1 equiv), Bu₃SnH (0.5 equiv), toluene, 80 °C, 4 h.

Scheme 299. Synthesis and Reactivity of Dinaphthothiepine Diimides

Reagents and conditions: (a) Na₂S, DMF, 60 °C; 3 h; (b) m-CPBA, DCM, −80 °C, 30 min, then rt, 1 h; (c) aq. H₂O₂, Na₂WO₄·2H₂O, MeN(n-C₈H₁₇)₃·HSO₄, phenylphosphonic acid, toluene/H₂O, 50 °C; (d) (1) Co(Cp*)₂, DCM, rt, 20 min, (2) chloranil.

Scheme 300. Synthesis of a Triaza Monkey Saddle

Reagents and conditions: (a)300.2, Pd₂(dba)₃, t-Bu₃P·HBF₄, K₂CO₃, THF/H₂O (1:1), 80 °C, 48 h; (b) AcOH/CHCl₃ (1:10), 80 °C, 18 h.

Scheme 301. Syntheses of Fused 1,4- and 1,5-Diazocines

Reagents and conditions: (a) palladium(II) trifluoroacetate (30 mol %), AgOAc (6.0 equiv), pivalic acid, 160 °C, 48 h; (b) neat, 145–150 °C.

Scheme 302. Syntheses of peri-Fused Oxocines via Annulative Coupling

Reagents and conditions: (a) Pd₂(dba)₃, t-Bu₃P·HBF₄, Cs₂CO₃, H₂O/t-amyl alcohol, 100 °C, 48 h; (b) Pd(OAc)₂ (5 mol %), AcOH, 100 °C, 12 h.

Scheme 303. Synthesis of Dinaphthodithiocine Diimide

Reagents and conditions: (a) Na₂S (1.2 equiv), DMF, rt, 3 h.

Scheme 304. Acenaphthylene-Fused Dithiaporphyrins

Reagents and conditions: (a) (1) NaOMe, THF, (2) MeOH, H₂SO₄; (b) LiAlH₄, diethyl ether; (c) MnO₂, DCM; (d) n-BuLi, TMEDA, 304.5a from 1-ethynyl-4-dodecyloxybenzene; 304.5b from 1-bromo-4-dodecyloxybenzene; 304.5c from ethynylbenzene; (e) (1) BF₃·Et₂O, pyrrole, (2) DDQ.

Scheme 305. Dihydropyracyloporphyrins

Reagents and conditions: (a) (1) TFA, DCM, 2 h, (2) DDQ, 1 h; (b) Ni(OAc)₂, 16 h, reflux; (c) benzaldehyde, BF₃·Et₂O, CHCl₃, N₂, 20 min, (2) DDQ, 20 min.

Scheme 306. [b]-Condensed Porphyrins Containing “Remote” peri-Fusion Points

Reagents and conditions: (a) (1) 306.2, TFA, CHCl₃, (2) Et₃N, DDQ; (b) Zn(OAc)₂·2H₂O, CHCl₃/MeOH; (c) Δ, 350 °C, reduced pressure, 0.5 to 3 h, quantitative yields.

Scheme 307. Synthesis of [b]-Fused Porphyrins Containing Pyrene Subunits

Reagents and conditions: (a) (1) TFA, DCM, N₂, 5 h, (2) DDQ, 3 h; (b) Pd(OAc)₂, CHCl₃/CH₃CN, reflux, 2 h; (c) (1) BF₃·Et₂O, DCM, N₂, 3 h, (2) DDQ, 5 h.

Scheme 308. Synthesis of Donor–Acceptor π-Extended Porphyrins

Reagents and conditions: (a) (1) benzaldehyde, p-TsOH·H₂O, CHCl₃/MeOH (100:1 v/v), (2) DDQ, rt; (b)^, Zn(OAc)₂, CHCl₃/MeOH; (c)^, Pd(OAc)₂, CHCl₃/MeOH; (d) HCl_conc, reflux; (e) 2,6-diisopropylaniline, AcOH, 160 °C; (f) 4-bromo-2,6-diisopropylaniline, AcOH, 160 °C; (g)308.7, AcOH, 160 °C; (h)308.8, Pd(dppf)Cl₂ (0.5 equiv), K₂CO₃, 120 °C, toluene/H₂O (4:1 v/v); (i) Pd(dppf)Cl₂ (1.5 equiv), K₂CO₃, 120 °C, toluene/H₂O (4:1, v/v).

Scheme 309. Synthesis of Donor–Acceptor Porphyrins with Mixed Ring Fusion Patterns

Reagents and conditions: (a) (1) 308.1a and 309.2 (+ 309.1, for 309.4a), p-TSA, CHCl₃/MeOH (100:1 v/v), 1 h, (2) DDQ, 2 h; (b) Zn(OAc)₂·2H₂O, CHCl₃/MeOH (3:1 v/v); (c) HCl, reflux, 24 h; (d) 2,6-diisopropylaniline, acetic acid, 20 h, reflux.

Scheme 310. Synthesis of a Rylene-Annulated Phthalocyanine

Reagents and conditions: (a) 3,4-dicyanobenzeneboronate pinacol ester, Pd(PPh₃)₄, K₂CO₃, THF/H₂O, reflux, 12 h; (b) hν, I₂, toluene, 95 °C, 48 h, Zn(OAc)₂, DBU, n-hexanol, 160 °C, MW, 1 h.

Scheme 311. Precise Control of π-Electron Magnetism in Metal-Free Porphyrins

Reagents and conditions: (a) Au(111), 295 °C; (b) Zn(OAc)₂, THF, reflux; (c) Au(111), 300 °C; (d) Au(111), 330 °C.

Scheme 312. Synthesis of a β–β′-Linked meso-Fused Carbatriphyrin(3.1.1) Dimer

Reagents and conditions: (a) PtCl₂ (6.5 equiv), chlorobenzene, reflux.

Scheme 313. Porphyrin-Based Conical Nanocarbons

Reagents and conditions: (a) gas phase, ΔE, N₂; (b) Pd(PCy₃)₂Cl₂ (8 equiv), DMAc/DBU (v/v 4:1), MW, N₂, 180 °C, 4 h.

Scheme 314. Synthesis of β,meso-Annulated Bacteriochlorins

Reagents and conditions: (a) (2-bromophenyl)boronic acid or (8-bromonaphthalen-1-yl)boronic acid, Pd(PPh₃)₄, K₂CO₃, toluene, DMF, 100 °C; (b) Pd(PPh₃)₄, SPhos, K₂CO₃, DMF, 80 to 100 °C, 6 h; (c) Pd(PPh₃)₄, PCy₃·HBF₄, K₂CO₃, DMF, 110 °C, 2 h.

Chart 30. meso-β-Pentannulated and Benzannulated Porphyrins

Scheme 315. Synthesis of Cyano-Substituted π-Extended Porphyrins

Reagents and conditions: (a) TBAP, DCM, glassy carbon or Pt cathode, controlled applied potential; (b) TBACN, CHCl₃, stir, 30 min.

Scheme 316. Synthesis of meso-Pyrrole Porphyrins

Reagents and conditions: (a) (1) DCM, TFA, p-tolualdehyde, rt, 16 h, (2) DDQ (2 equiv); (b) EtONa (10 equiv), Ph₃P⁺CH₂PhCl^– or Et₄N⁺Cl^– (10 equiv), EtOH, then addition of 316.2a or 316.2b, 24 h; (c) (1) TFA (10%) followed by neutralization with Et₃N, (2) Ni(OAc)₂, DMF, reflux, 1 h; (d) TFA/H₂SO₄ neutralization with Na₂CO₃, 2 h; (e) CHCl₃/MeOH, Zn(OAc)₂, 1 h; (e) THF, nBu₄N⁺F^–, N₂.

Scheme 317. Synthesis of Diarylamine-Fused Porphyrins

Reagents and conditions: (a) DDQ (10 equiv), Sc(OTf)₃ (10 equiv), ClCH₂CH₂Cl/MeNO₂ 70 °C, 1 h; (b) DDQ (10 equiv), FeCl₃ (10 equiv), DCM/MeNO₂, rt; (c) (1) FeCl₃ (10 equiv), DCM/MeNO₂, 70 °C, 1 h, (2) HCOOH, NEt₃, Pd₂(dba)₃, SPhos, toluene, 120 °C, 1 h; (d) TFA/conc. H₂SO₄; (e) Zn(OAc)₂·2H₂O, DCM; (f) (1) p-tolylmagnesium bromide, toluene, (2) 3 M HCl_aq; (g) BAHA (1.1 equiv), DCM, rt, 10 min; (h) 2-chloro-1,3-bis(methoxycarbonyl)guanidine (2.2 equiv), CHCl₃, 0 °C (10 min) to rt, 2.5 h for 317.7a and 7 h for 317.7a; (i) BAHA (1.1 equiv), DCM, rt, 10 min for 317.7a and 5 min for 317.7a.

Scheme 318. Synthesis of Diarylamine-Fused Subporphyrins and Porphyrin Dimers

Reagents and conditions: (a)318.2a or 318.2b (3 equiv), NaOt-Bu (12 equiv), DMF, 100 °C, 15 min; (b)318.2a (3 equiv), DMF, rt, 30 min; (c) NaOt-Bu (12 equiv), DMF, 100 °C, 10 min; (d)318.2a or 318.2c (2.5 equiv), NaOt-Bu (10 equiv), DMF, 100 °C; (e) BAHA (6.0 equiv), DCM, rt, 10 min; (f) BAHA (6.0 equiv), DCM, rt, 15 min, then H₂NNH₂·H₂O.

Scheme 319. Synthesis of Diarylamine-Fused Porphyrin Dimers

Reagents and conditions: (a)t-BuONa (11 equiv), DMF, 60 °C, 10 h; (b) Pd(OAc)₂, PCy₃·HBF₄, pivalic acid, K₂CO₃ (10 equiv), DMA, 140 °C, 13 h.

Scheme 320. Synthesis of a 1,5-Naphthyridine-Fused Porphyrin Dimer

Reagents and conditions: (a) PtCl₂, toluene, rt, 3 h, and then, PbO₂, DCM, rt, 1 h; (b) NaBH₄, DCM/MeOH, rt, 15 min; (c) PbO₂, DCM, rt, 5 min.

Scheme 321. Quinolino-Fused Porphyrins

Reagents and conditions: (a) NaBH₄, 10% Pd/C, N₂, CH₃CN/EtOH, rt, 10 min; (b) CH₃CN, 1 h, reflux; (c) TFA, conc. H₂SO₄.

Scheme 322. Oxidative Coupling of Enaminoporphyrin

Reagents and conditions: (a) Fe(phen)₃(PF₆)₃, Na₂CO₃, DCM, rt; (b) PIFA, Na₂CO₃, DCM, rt.

Scheme 323. Synthesis of Fused meso-Aminoporphyrins

Reagents and conditions: (a) arylamine (5 equiv), Pd(OAc)₂, DPEPhos, Cs₂CO₃, THF, 65 °C, 3 h; (b) DDQ, DCM; (c) DDQ, DCM, TFA; (d) NaBH₄, THF; (e) HCl; (g) DCM; (f) TBAF, THF.

Scheme 324. Quinoline-Annulated Porphyrins

Reagents and conditions: (a) pyridine, reflux, 48 h; (b) BBr₃, DCM; (c) Me(OCH₂CH₂)₄OMs or Me(OCH₂CH₂)₁₂OMs, Cs₂CO₃, DMF, 90 °C; (d) (1) Zn(OAc)₂·2H₂O, DCM/MeOH, (2) 324.3 (1 equiv), Na₂CO₃, copper(I) thiophene-2-carboxylate, CH₃CN, 50 °C, (3) HCl.

Scheme 325. Synthesis of Quinoline-Annulated Chlorin and Derivatives

Reagents and conditions: (a) OsO₄, pyridine, CHCl₃, rt; (b) H₂S, CHCl₃, rt; (c) DMP, DCM, rt; (d) DCM, CTAP; (e) NaIO₄/silica, EtOH, or MeOH.

Scheme 326. Intramolecular Oxidative C–N Coupling of Pyridin-2-ylthio-meso-substituted Porphyrins

Reagents and conditions: (a) (1) PIFA (1 equiv), DCM, rt, (2) anion exchange: X = CF₃COO to PF₆.

Scheme 327. Synthesis of meso-N/O-Heteroarene-Fused Porphyrins via a [4 + 2] Oxidative Annulation Strategy

Reagents and conditions: (a) Standard conditions for 348.6–8: 348.5 (0.2 mmol), [Cp*RhCl₂]₂ (5 mol %), AgSbF₆ (20 mol %), THF (0.5 mL), 100 °C, N₂, 24 h; (b) standard conditions for 348.9–10: 348.5 (0.2 mmol), [Cp*RhCl₂]₂ (5 mol %), AgSbF₆ (20 mol %), Ag₂O (2.0 equiv), NaSbF₆ (2.0 equiv), DCE (0.5 mL), 120 °C, N₂, 24 h; (c) 348.5 (0.2 mmol), [Cp*RhCl₂]₂ (5 mol %), AgSbF₆ (20 mol %), Ag₂O (2.0 equiv), DCE, or 1,4-dioxane (0.5 mL), 120 °C, N₂, 24 h; (d) [Cp*RhCl₂]₂ (5 mol %), AgSbF₆ (20 mol %), Ag₂O (2.0 equiv), DCE, or 1,4-dioxane (0.5 mL), 120 °C, N₂; (e) FeCl₃ (10 equiv), DDQ (10 equiv), DCM/MeNO₂.

Scheme 328. Synthesis of Doubly and Triply Fused Subporphyrin Dimers

Reagents and conditions: (a) (1) NBS, CHCl₃, 0 °C, 3 h, (2) Ni(cod)₂, 1,5-cod, DMF, 80 °C, 3 h; (b) PPh₃ (10 equiv), toluene, 120 °C, 3 h; (c) BAHA (4.0 equiv), DCM, rt, 1 h, then H₂NNH₂·H₂O; (d) dppp (5 equiv), toluene, 120 °C, 1 h.

Scheme 329. Synthesis of a Trimethylenemethane Diradical Fused with Three Porphyrins

Reagents and conditions: (a)i-PrMgCl·LiCl (1.1 equiv), THF, −40 °C, then 329.1 (0.4 equiv), −40 °C to rt, 2 h; (b) (1) 25% H₂SO₄, 1,2-dichloroethane, 60 °C, 11 h, (2) DDQ (10 equiv), DCM, rt, 15 min, (3) ascorbic acid (10 equiv), DCM/MeOH.

Scheme 330. Synthesis of Naphthoquinodimethane-Bridged Porphyrin Dimers

Reagents and conditions: (a) (1) 2-mesitylmagnesium bromide, dry THF, 8 h, rt, (2) BF₃·OEt₂, dry DCM, 5 min, rt; (b) DDQ, dry toluene, rt.

Scheme 331. Synthesis of Singly and Doubly Naphthalene-Fused Porphyrins and Anthracene-Bridged Porphyrin Dimers

Reagents and conditions: (a) (1) 2-mesitylmagnesium bromide, dry THF, rt, (2) BF₃·OEt₂, dry DCM, (3) DDQ, DCM; (b) t-BuOK, THF.

Scheme 332. Synthesis of Bacteriochlorins Bearing Fused Quinoxaline, Benzimidazole, and Perimidine Aromatic Rings

Reagents and conditions: (a) LiOH/H₂O, THF, 24 h; (b) O₂; (c) 1,2-phenylenediamine hydrochloride, pyridine, TFA, reflux; (d) 1,8-diaminonaphthalene hydrochloride, pyridine, TFA, reflux; (e) CH₂N₂, DCM, N-methyl-N-nitroso-p-toluenesulfonamide, rt, overnight.

Chart 31. Porphyrin Oligomers Linked by Metal Ions

Scheme 333. Synthesis of Boron(III) Carbazosubphthalocyanines

Reagents and conditions: (a) (1) EtOH, reflux, (2) BF₃·Et₂O, DBU, 1-chloronaphthalene, 150 °C.

Scheme 334. Synthesis of π-Extended Carbazole-Based Porphyrins

Reagents and conditions: (a) (1) NBS, CHCl₃, 0 °C, (2) Bu₃SnC≡CR², Pd(PPh₃)₄, toluene, reflux; (b) PtCl₂, toluene, reflux; (c) MnO₂, DCM, rt; (d) Cu(OAc)₂·2H₂O, pyridine, toluene, air, rt; (e) Na₂S·9H₂O, toluene, 2-methoxyethanol, reflux; (f) PbO₂, DCM, rt.

Scheme 335. Carbazole-Based Porphyrins

Reagents and conditions: (a)^, MnO₂, DCM, rt.

Scheme 336. Synthesis of Asymmetric Carbazole-Based Porphyrins and Their Oligomers

Reagents and conditions: (a) (1) 336.2a or 336.2b, p-TSA (0.2 equiv), DCM, rt, dark, 1 h, (2) DDQ (1 equiv), 10 min; (b) (1) 336.2c, CF₃COOH (1 equiv), DCM, rt, dark, 90 min, (2) DDQ (2 equiv), 10 min; (c) (1) Pd₂(dba)₃, SPhos, CsF, Cs₂CO₃, reflux, 48 h, (2) MnO₂; (d) NBS (0.9 equiv), CHCl₃; (e) NBS (3.7 equiv), CHCl₃; (f) (Bpin)₂ (2.9 equiv), Pd(dppf)Cl₂, KOAc, 1,4-dioxane, reflux; (g) (Bpin)₂ (9.8 equiv), Pd(dppf)Cl₂, KOAc, 1,4-dioxane, reflux; (h)336.6a/336.7a (1:1), Pd₂(dba)₃, PPh₃, CsF, Cs₂CO₃, toluene/DMF, reflux, 48 h; (i)336.6a/336.7b (1:0.5), Pd₂(dba)₃, PPh₃, CsF, Cs₂CO₃, toluene/DMF, reflux, 48 h.

Scheme 337. Thiophene-Bridged Carbazole-Based Diporphyrins

Reagents and conditions: (a) PbO₂, DCM; (b) Na₂S·9H₂O, p-xylene, 2-methoxyethanol, reflux.

Scheme 338. Directly Linked and Fused Carbazole-Based Diporphyrins

Reagents and conditions: (a) PbO₂, DCM.

Scheme 339. Synthesis of Carbenaporphyrins

Reagents and conditions: (a) CuSO₄·5H₂O, tris((1-benzyl-4-triazolyl)methyl)amine, sodium ascorbate, Et₃N, THF, Ar; (b) 2Me₃OBF₄, DCM; (c) LiHMDS (6.6 equiv), THF-d₈; (d) ScCl₃(THF)₃, THF-d₈; (e) LiCp, THF-d₈; (f) LiHMDS, THF, LiCp.

Scheme 340. Synthesis of Bisanthracene-Fused Porphyrins

Reagents and conditions: (a) NBS, DCM/MeOH (10:1, v/v); (b) 9-anthraceneboronic acid, Pd(PPh₃)₄, K₂CO₃, toluene/DMF (5:1, v/v), 120 °C; (c) TfOH, DDQ, DCM.

Scheme 341. Synthesis of Diphenylmethane-Fused Porphyrins

Reagents and conditions: (a)^, (2-R¹-C₆H₄)₂CHLi (2.0 equiv), THF, −98 °C to rt, 2 h; (b)^, Pd(OAc)₂, PCy₃·HBF₄, K₂CO₃ (5.0 equiv), toluene, reflux, overnight; (c) H₂SO₄/CF₃CO₂H, 0 °C to rt, 45 min; (d) BAHA, CDCl₃, rt; (e) cobaltocene, [D₈]THF, rt.

Scheme 342. Synthesis of Di-peri-dinaphthoporphyrin Porphyrins

Reagents and conditions: (a) CBr₄, PPh₃, toluene, 80 °C, 12 h; (b) M = Ni: Ni(acac)₂, toluene, reflux, 3 h; M = Zn: Zn(OAc)₂·2H₂O, DCM, MeOH, rt, 1 h; (c) tributyl(phenylethynyl)tin, Pd₂(dba)₃, P(2-furyl)₃, toluene, 80 °C, 1 h; (d) PtCl₂ or Pt(MeCN)₂Cl₂, toluene, 90 °C, 12 h; (e) HCl, DCM, quantitative yield.

Scheme 343. Synthesis of Diphenylborane-Fused Porphyrins

Reagents and conditions: (a) BBr₃, o-dichlorobenzene, 80 °C; (b) TFA/H₂SO₄/DCM, 0 °C; (c) PdCl₂(PhCN)₂, PhCN, 140 °C; (d) Cu(OAc)₂, DCM/MeOH, rt; (e) Zn(OAc)₂·2H₂O, DCM/MeOH, rt.

Scheme 344. Synthesis of Diphenylphosphine-Fused Porphyrins

Reagents and conditions: (a) LiPPh₂, THF, rt; (b) H₂O₂, DCM, rt; (c) Pd(OAc)₂, PCy₃·HBF₄, t-BuCO₂H, K₂CO₃, DMA, 120 °C; (d) conc. H₂SO₄, TFA, 0 °C, and then, Zn(OAc)₂·2H₂O, DCM/MeOH, rt; (e)^, HSiCl₃, toluene, reflux; (f) 5-methyl-2-thienylzinc chloride lithium chloride, Pd₂(dba)₃, RuPhos, THF, reflux; (g) PBr₃, ZnI₂, o-dichlorobenzene, 180 °C; then, H₂O₂; (h) HSiCl₃, toluene, rt.

Scheme 345. Synthesis of Triply Fused Porphyrin–Nanographene Conjugates

Reagents and conditions: (a) (1) Pd(PPh₃)₄, K₂CO₃, toluene/DMF (1:1, v/v), 110 °C, 36 h, (2) Pd(PPh₃)₄, triethylamine, formic acid, toluene, 100 °C, 2 h; (b) DDQ, DCM/triflic acid (100:1, v/v), rt, 10 h.

Scheme 346. Synthesis of Doubly and Quadruply Phenylene-Fused Porphyrins

Reagents and conditions: (a) DDQ, FeCl₃, DCM/MeNO₂, rt; (b) DDQ, FeCl₃, DCM/MeNO₂, rt, 4 h; (c) NCS, CuCl, DMF/toluene, 80 °C, 1 h; (d) NEt₃/HCOOH, Pd₂(dba)₃, SPhos, toluene, 120 °C, 13 h; (e) Ni(cod)₂, DMF, 100 °C, 9 h; (f) (1) TFA/conc. H₂SO₄, 0 °C, 30 min, (2) Zn(OAc)₂·2H₂O, DCM, MeOH, rt, 1 h; (g) DDQ, Sc(OTf)₃, toluene, 70 °C, 1 h.

Chart 32. Porphyrin Nanobelt from Triply Linked Porphyrin Tapea

Scheme 347. Synthesis of Triply Linked Corrole Dimers

Reagents and conditions: (a) DDQ (3.5 equiv), CHCl₃ (ca. 0.03 mM), reflux, 30 min; (b)p-chloranil (1 equiv), CHCl₃, reflux, 15 min; (c) DDQ (2 equiv), CHCl₃, reflux, 30 min; (d) NaBH₄, THF/MeOH; (e) air; (f)^, M = Zn: Zn(OAc)₂·2H₂O, CHCl₃, reflux, 20 h; M = Cu: Cu(acac)₂ (30 equiv), toluene/MeOH, reflux, 20 h; (g) AgBF₄ (2 equiv), DCM/EtNO₂, rt, 5 min; (h) Co(OAc)₂·2H₂O, pyridine, 100 °C, 15 min; (i) DDQ (3.5 equiv), CHCl₃, reflux, 30 min; (j) p-chloranil (1 equiv), CHCl₃, reflux, 3.5 h.

Scheme 348. Synthesis of Face-to-Face Dimers and Monomeric Gallium(III) Corrole Tapes

Reagents and conditions: (a) (1) NaBH₄, THF/MeOH, (2) GaCl₃ (50 equiv), pyridine, reflux, workup; (b) R¹ZnI·LiCl (20 equiv), TMSCl (40 equiv), THF, reflux.

Scheme 349. Synthesis of Triple Decker Complexes Containing a Triply Linked Diporphyrin

Reagents and conditions: (a) LiHMDS (6.6 equiv), 1,2,4-trichlorobenzene 120 °C, 1 h; (b) 349.3a (2 equiv) or 349.3a (2 equiv), 1,2,4-trichlorobenzene 120 °C, 2 h; (c) DBU (116 equiv), DCM, rt, 1 h; (d) CH₃COOH (excess), DCM, rt, N₂, 1 h

Scheme 350. Synthesis of Porphyrin Tapes

Reagents and conditions: (a) (1) 350.3a, CH₃SO₃H (15 mol %), (2) DDQ (3 equiv), DCM, 0 °C, 2 h, then rt 15 min; (b) (1) 350.3b, p-TsOH·H₂O (1 equiv), (2) DDQ (6 equiv), DCM, 0 °C, 2 h, then rt 15 min; (c) (1) H₂SO₄, TFA, rt, 5 days, (2) Zn(OAc)₂·2H₂O (60 equiv), CHCl₃/MeOH, 50 °C, o/n; (d) (1) H₂SO₄, TFA, 0 °C, 30 min, (2) Zn(OAc)₂·2H₂O (60 equiv), CHCl₃/MeOH, 50 °C, o/n; (e) DDQ (8 equiv), Sc(OTf)₃ (8 equiv), toluene, 100 °C, 5 h; (f) DDQ (8 equiv), Sc(OTf)₃ (8 equiv), toluene, 80 °C, 4 h; (g) H₂SO₄, TFA, 0 °C, 30 min, (2) Zn(OAc)₂·2H₂O (40 equiv), CHCl₃/MeOH, 50 °C, o/n; (h) DDQ (5 equiv), Sc(OTf)₃ (5 equiv), toluene, rt, 3 h; (i) DDQ (12 equiv), Sc(OTf)₃ (12 equiv), toluene, 80 °C, 3 h.

Scheme 351. Synthesis of Carbonyl- and Methylene-Containing Porphyrin Arch Tapes

Reagents and conditions: (a) DDQ/Sc(OTf)₃ (5 equiv), toluene, 60 C, 2–3 h; (b) NaBH₄, CeCl₃, DCM/MeOH, −80 °C; (c) (1) HBF₄·OEt₂, DCM, rt, 10 min, (2) BH₃·NEt₃, rt, 10 min; (d) DDQ/Sc(OTf)₃ (15 equiv), toluene, 60 °C, 5 h.

Scheme 352. Synthesis of 1,2-Phenylene- and Sulfone-Containing Porphyrin Arch-Tape Dimers

Reagents and conditions: (a) Palau′Chlor, CHCl₃, rt, 6 h; (b) Ni(cod)₂, 1,5-cyclooctadiene, DMF, 100 °C, 9 h; (c) DDQ, Sc(OTf)₃, toluene, 80 °C, 2 h; (d) DDQ, Sc(OTf)₃, toluene, 60 °C, 1 h; (e) H₂O₂, NaWO₄·2H₂O, MeN(nOct)₃·HSO₄, PhP(O)(OH)₂, toluene, 50 °C, 13 h; (f) AuCl₃, AgOTf, (CHCl₂)₂, 80 °C, 30 min.

Scheme 353. Electropolymerization of Metalloporphyrins

Reagents and conditions: (a) electrochemical potential, E_app = 0.35 V, CH₃CN; (b)^,E_app > 0.65 V, in TBAPF₆/CH₃CN.

Scheme 354. On-Surface Synthesis of Singly and Doubly Porphyrin-Capped Graphene Nanoribbon Segments

Reagents and conditions: (a) 200–350 °C on the Au(111) surface; (b) 10,10′-dibromo-9,9′-bianthracene, 200–350 °C, Au(111).

Scheme 355. Synthesis of β-Substituted Dithiaporphyrins by a Heck Reaction

Reagents and conditions: (a) styrene, Pd(OAc)₂, K₂CO₃, PPh₃, DMF/toluene (1:1, v/v), reflux, 1 h.

Scheme 356. On-Surface Site-Selective Cyclization of Corrole Radicals

Reagents and conditions: (a) Ag(111), 330 K; (b) Ag(111), 430 K.

Scheme 357. Synthesis of Quadruply Ring-Fused Porphyrinsa

Reagents and conditions: (a) TFA, CHCl₃; (b) NBS (5 equiv), CHCl₃; (c) NBS (1.9 equiv), CHCl₃; (d) (1) phenylboronic acid, Pd(PPh₃)₄, K₂CO₃, (2) TFA, NaHCO₃, (3) Zn(OAc)₂·2H₂O; (e) 2,4,6-trimethylphenylboronic acid, Pd(PPh₃)₄, K₂CO₃; (f) TFA, CHCl₃.

Scheme 358. Synthesis of π-Extended Derivatives from Enone-Substituted Chlorins

Reagents and conditions: (a) NH₄OAc, acetic acid, N₂, reflux.

Scheme 359. Phosphole-Fused and Pyrrole-Fused Dehydropurpurins

Reagents and conditions: (a) (1) Ti(Oi-Pr)₄−i-PrMgCl, (2) PhPCl₂, (3) H₂O₂ or S₈, Et₂O; (b) conc. H₂SO₄, CF₃COOH; (c) Zn(OAc)₂·2H₂O, DCM/MeOH; (d) Lawesson’s reagent, toluene; (e) P(NMe₂)₃, toluene; (f) air; (g) aniline, PdCl₂, Et₃N, toluene/DMSO.

Scheme 360. Synthesis of Etheno-Fused Diporphyrin Dications

Reagents and conditions: (a) Ni(cod)₂, 2,2′-bipyridyl, THF; (b) BAHA (4 equiv), DCM, rt; (c) CoCp₂ (4 equiv), DCM, rt.

Scheme 361. Synthesis of Singly and Doubly N-C_Ar-Fused Confused Corroles

Reagents and conditions: (a) DDQ (1 equiv), DCM; (b) NBS, DCM; (c) toluene, reflux; (d) DMF, 30 °C.

Scheme 362. Synthesis of β -to- β-Linked meso-Aminoporphyrin Dimers

Reagents and conditions: (a) Ni(cod)₂, DMF, 100 °C; (b)^, I₂, AgNO₂, DCM/MeCN, rt; (c)^, NaBH₄, Pd/C, DCM/MeOH, rt; (d) PhICl₂, CHCl₃, 0 °C; (e) PbO₂, DCM, rt; (f) PbO₂, DCM, rt, and then, SnCl₂, DCM, rt; (g) 4-tert-butylaniline, Pd-PEPPSI-IPr, NaOt-Bu, toluene, 120 °C.

Scheme 363. Oxidative Reactivity of meso-Amino meso-to-β-Linked Nickel(II) Aminoporphyrin

Reagents and conditions: (a) PbO₂ (100 equiv), DCM, rt, 12 h; (b) MnO₂ (100 equiv), DCM, rt, 16 h.

Scheme 364. Naphthobipyrrole Macrocycles

Reagents and conditions: (a) appropriate aldehyde, TFA, DCM, (2) DDQ, TEA; (b) TFA, cobaltocene, THF-d₈; (c) TEA; (d) catechol, K₂CO₃, NMP, 100 °C, 6 h.

Scheme 365. Synthesis of a Cyclooctatetraene-Bridged Gallium(III) Corrole Dimer

Reagents and conditions: (a) 1,2,4-trichlorobenzene, reflux, 24 h; (b) (1) GaCl₃, pyridine, N₂, (2) DCM, n-heptane; (c) pyridine.

Chart 33. Porphyrinoids Containing Polycyclic Thiophene-Based Subunits

Scheme 366. Synthesis of Dibenzo[g,p]chrysene-Fused Bisdicarbacorrole

Reagents and conditions: (a)^, (1) pentafluorobenzaldehyde, BF₃·OEt₂, DCM, rt, (2) DDQ, rt; (b) Cu(OAc)₂·H₂O (73.8 equiv), CHCl₃, reflux, 48 h; (c)^, Pd(PhCN)₂Cl₂ (3 equiv for 366.5; 2 equiv for 366.6; 15 equiv for 366.7), PhCN, 180 °C.

Scheme 367. Expanded Carbaporphyrins Incorporating Aza-[5]helicene Motifs

Reagents and conditions: (a) (1) p-nitrobenzaldehyde, BF₃·OEt₂, CHCl₃, 2 h, (2) DDQ, 10 min; (b) BF₃·OEt₂, toluene, triethylamine, reflux, 90 min, (2) triethylamine.

Scheme 368. Phenanthriporphyrin

Reagents and conditions: (a) H₂SO₄, 0 to 40 °C, 28 h; (b) air oxidation; (c) HBF₄·Et₂O.

Scheme 369. Phenanthrene- and Naphthalene-Containing Porphyrinoid Macrocycles

Reagents and conditions: (a) Δ, amine; (b) (1) BF₃·OEt₂, TEA, toluene, reflux, 3 h, (2) TEA.

Scheme 370. Anthracene- and Naphthalene-Based Carbaporphyrins

Reagents and conditions: (a) (1) BF₃·OEt₂, DCM, 1 h, (2) p-chloranil, 20 min; (b) Pd(OAc)₂, DCM/CH₃CN; (c) dimethyl acetylenedicarboxylate, o-DCB, 145 °C.

Scheme 371. Hybrid Porphyrinoid Macrocycles

Reagents and conditions: (a) (1) BF₃·OEt₂, C₆F₅CHO, (2) DDQ; (b) PCl₃, TEA, toluene, reflux, 1 h; (c) PdCl₂, CHCl₃/CH₃CN, reflux.

Scheme 372. Synthesis of 28-Hetero-2,7-naphthiporphyrins

Reagents and conditions: (a) (1) phenylmagnesium bromide, THF, (2) H₃O⁺; (b) (1) pyrrole, BF₃·OEt₂, CHCl₃, N₂, reflux, 48 h, (2) triethylamine; (c) (1) BF₃·OEt₂, CHCl₃, (2) DDQ, 15 min; (d) Zn(Hg), toluene, N₂; (e) O₂; (f) PCl₃, TEA, toluene, reflux, 80 min.

Chart 34. Porphyrin–Pyrrolylene Supermacrocycles

Chart 35. Porphyrin Nanohoops and Nanorings

Scheme 373. Internally Strapped Porphyrinoid Macrocycles

Reagents and conditions: (a) Zn/H⁺; (b) O₂; (c) Pd(OAc)₂, DMF.

Chart 36. Edge-Sharing π-Extension in Porphyrinoids with Multiple Cavities

Scheme 374. Synthesis of a Porphyrin(2.1.2.1)-Based Nanobelt

Reagents and conditions: (a) (1) RCHO, BF₃·Et₂O (5–70 mol %), (2) DDQ, (3) Ni(OAc)₂.

Scheme 375. Phthalocyanine-Based Pyrazine-Linked Conjugated Two-Dimensional Covalent Organic Frameworks

Reagents and conditions: (a) dimethylacetamide/o-dichlorobenzene (1:1, v/v), H₂SO₄, 202 °C, 10 days; (b) 1-methyl-2-pyrrolidone/mesitylene (2:1, v/v), p-TSA (3.5 M), 150 °C, 3 days.

Scheme 376. Benzene-Fused Doubly N-Confused Porphyrins

Reagents and conditions: (a)tert-butyl 5-acetoxymethyl-3,4-diethylpyrrole-2-carboxylate, catalytic p-TsOH·H₂O, AcOH, rt, 3 h; (b) TFA, N₂, CH₂(OMe)₂, DCM, p-chloranil.

Scheme 377. N-Fused Pentaphyrins and Their Reactivity

Reagents and conditions: (a) (1) p-TsOH·H₂O, DCM, N₂, 90 min, (2) DDQ, 1 h; (b) CH₃OH, 25 °C, 4 h.

Scheme 378. Synthesis of Doubly N-Fused [24]Pentaphyrin and Its Reactivity

Reagents and conditions: (a) MeSiCl₃ (100 equiv), DIPEA (300 equiv), DMF, 80 °C, 14 h; (b) KHCO₃ (4 equiv), excess aq. H₂O₂, THF, rt, 45 min; (c) TBAF, CD₂Cl₂; (d) H₃O⁺.

Scheme 379. Palladium Insertion-Triggered Reactivity of N-Fused Pentaphyrin

Reagents and conditions: (a) Pd(CF₃CO₂)₂ (5 equiv), THF, reflux; (b) DDQ (1.2 equiv), Sc(OTf)₃ (0.7 equiv), toluene, rt.

Scheme 380. Oxidative Reactivity and Ring Fusion in Twisted Thianorhexaphyrin

Reagents and conditions: (a) DDQ, DCM; (b) p-chloranil, DCM; (c) O₂, Et₃N/MeCN; (d) H₂O₂/AcOH, THF; (e) m-CPBA, DCM; (f) PPh₃, DCM.

Scheme 381. N-Fused Heptaphyrins

Reagents and conditions: (a) (1) pentafluorobenzaldehyde, BF₃·H₂O, DCM, 3 h, rt, (2) DDQ, 1 h, rt.

Scheme 382. Synthesis of N²¹,N²²-Carbamide-corroles

Reagents and conditions: (a) COCl₂, toluene, 0 °C (10 min), then pyridine, toluene, N₂, reflux (15 min); (b) (NH₄)₂CO₃ (excess), CHCl₂, pyridine, 110 °C, 3 h; (c) Rh₂(CO)₄Cl₂, LiHMDS, benzene, reflux; (d)382.3a, PPh₃, benzene.

Scheme 383. Synthesis of Boron(III) and Phosphorus(V) N-Fused p-Benziporphyrin

Reagents and conditions: (a) PCl₃, Et₃N, H₂O, toluene, 3 h; (b) PhBCl₂, Et₃N, toluene, 5 h; (c) Br₂, CHCl₃; (d) Br₂, DCM, or DDQ/MeOH

Scheme 384. Bisphenanthroline peri-Fused Cyclophanes and Their Complexes

Reagents and conditions: (a) NH₃, 280–300 °C, 36 h, (b) FeCl₃, N(n-Bu)₃, DMF, 170 °C, 36 h, (c) EtOH, 48 h, Soxhlet, (d) FeBr₂, DMF; (e) H₂O under air, rt.

Scheme 385. Shape-Persistent Macrocycles Containing peri-Condensed Pyridine Rings

Reagents and conditions: (a) AIBN, NBS (2.5 equiv), CCl₄, 77 °C, 5 h; (b) Na₂CO₃, 1,4-dioxane, 80 °C, 14 h; (c) TFA (10 equiv), dichloroethane, 70 °C, 18 h; (d) n-butyl vinyl ether (10 equiv), MeCN, 45 °C, 25 h; (e) n-butyl vinyl ether (10 equiv), degassed CH₃CN, rt; (f) air; (g) 2,3-dihydrofuran (50 equiv), MeOH, 25 °C, 24 h; (h) nBuLi, THF, −78 to 25 °C, 16 h.

Scheme 386. Shape-Persistent Macrocycles Containing peri-Condensed Pyridine Rings

Reagents and conditions: (a) (1) KOH, MeOH/THF (2:1 v/v), rt, 24 h, (2) Pd(PPh₃)₄, CuI, NEt₃/THF (1:2, v/v), 50 °C, 24 h.

Chart 37. Nitrogen-Doped Phenine Nanotubes

Scheme 387. Oxidative Fusion Reactions of ortho-Phenylene-Bridged Cyclic Hexapyrrole and Hexathiophene

Reagents and conditions: (a) DDQ, Sc(OTf)₃, toluene, reflux.

Scheme 388. Synthesis and Oxidation of [n]Cyclo-1,8-carbazolylenes

Reagents and conditions: (a) slow addition of 388.2 over 1 h to Ni(cod)₂ (250 mol %), cod (250 mol %), 2,2′-bipyridyl (150 mol %), THF, 80 °C, then, 80 °C, 1 h; (b) n-BuLi, toluene, −80 °C, then 0 °C, 30 min, (2) BBr₃, −80 °C, then rt, 3 h; (c) PhSiCl₃, Et₃N, 1,2-DCE, 90 °C, 12 h; (d) PCl₃, Et₃N, 1,2-DCE, 90 °C, 16 h; (e) m-CPBA, DCM, 30 min; (f) DDQ (1.5 equiv), CHCl₃ stabilized by 0.3–1.0% EtOH, rt; (g) DDQ (2.0 equiv), EtOH-free CHCl₃, rt, 95%.

Chart 38. [4]Cyclo(2,7)carbazoles and Related Systems

Scheme 389. peri-Fused Dibenzofuran-, Dibenzothiophene-, and Carbazole-acetylene Macrocycles

Reagents and conditions: (a) (1) TBAF, THF, rt, 1 h, (2) 389.2a, 389.2b, or 389.2c, Pd(PPh₃)₄, CuI, NEt₃/THF (1:1 v/v), rt, 24 h.

Scheme 390. Synthesis of a Carbazole-Based Cyclophane

Reagents and conditions: (a) TiCl₄, Zn, pyridine, dioxane, reflux; (b) CHCl₃ or CDCl₃, 365 nm, 72 h.

Scheme 391. Synthesis of an Imine-Bridged Carbazole-Based Cyclophane

Reagents and conditions: (a) EtOH, reflux, 48 h; (b) EtOH, CH₃CN, reflux, 36.5 to 38 h.

Scheme 392. Synthesis of Tricarbazolotriazolophane Macrocycles

Reagents and conditions: (a)^, CuSO₄, sodium ascorbate, TBTA, 2:1:1 THF/EtOH/H₂O, 55–70 °C, 6–7 h; (b) (1) Me₃OBF₄, DCM, rt, 4 d, (2) NH₄PF₆, H₂O/acetone, rt, 2 h; (c) K₂CO₃, 2:1 THF/MeOH, rt, 1 h; (d) (1) NaNO₂, TsOH, THF/H₂O, 0 °C, 30 min, (2) NaN₃, 0 °C to rt, 1.5 h.

Scheme 393. Shape-Persistent Macrocycles Containing peri-Condensed Pyridine Rings

Reagents and conditions: (a) NH₄OAc, dioxane/mesitylene (1:4, v/v) 150 °C, 5 days; (b) R¹-Br, NaH, THF, 65 °C, 2 days.

Chart 39. Sulfur-Containing peri-Fused Macrocycles

Scheme 394. Sulfur-Containing peri-Fused Macrocycles

Reagents and conditions: (a) acetylene, Pd(PPh₃)₄, CuI, Et₃N, THF, 70 °C, 3 h; (b)^, Na₂S·H₂O, toluene, 2-methoxyethanol, 150 °C, 12 h; (c) TFA, DCM, H₂O, rt, 12 h; (d)p-TsOH, AcOH, EtOH, DCM, 110 °C, 12 h.

Scheme 395. Phenoxathiin- and Phenazine-Containing Cyclophanes

Reagents and conditions: (a) Cs₂CO₃, DMSO, 120 °C, 26 h; (b) (1) Tf₂O, dichloroethane, rt, 1 h, (2) pyridine, rt, 10 h; (c) BBr₃, DCM, −15 °C to rt, 20 h; (d) (1) CF₃SO₃H, P₂O₅, rt, 26 h, (2) pyridine/H₂O (1:1, v/v), 105 °C, 18 h; (e) (1) nBuLi, THF, −5 °C, 1 h, (2) CH₃CH₂I, rt, 24 h; (f) BBr₃, DCM, −10 °C to rt, 20 h; (g) 395.1b, CuI, Cs₂CO₃, N,N-dimethylglycine, DMAc, 150 °C, 48 h; (h) (1) CF₃SO₃H, 80 °C, 48 h, (2) pyridine/H₂O (1:1, v/v), 105 °C, 15 h.

Scheme 396. Sulfur-Containing peri-Fused Macrocycles

Reagents and conditions: (a) Ni(cod)₂, THF, 65 °C; (b) SnCl₂, DCM, rt; (c)p-chloranil, rt, 2 h.

Scheme 397. Oxygen-Containing peri-Fused Macrocycles

Reagents and conditions: (a) (1) PtCl₂(cod), THF, reflux, 2 days, (2) PPh₃, toluene, reflux, 3 h.

Chart 40. Polycyclic Arylamine Cyclophanes

Scheme 398. Oxidation of a Tetraazacyclophane to a Diradical Dication

Reagents and conditions: (a) 2 equiv of Ag[Al(OC(CF₃)₂CH₃)], DCM, rt, 1 day.

Scheme 399. Polycyclic Arylamine Cyclophanes

Reagents and conditions: (a) BF₃·OEt₂, DCM; (b) DDQ, toluene.

Scheme 400. Conjugated Macrocyclic Hexabenzocoronene Dimers

Reagents and conditions: (a) PbO₂, CDCl₂CDCl₂, rt, 5 min.

Scheme 401. Twisted Macrocycle with a Nitrogen Bridge

Reagents and conditions: (a) BF₃·Et₂O, MS4 Å, 10:1 DCM/HFIP, rt, 3 h; (b) aniline, t-BuONa, Pd₂(dba)₃, P(t-Bu)₃, toluene, 90 °C, 16 h.

Scheme 402. Oxygen-Containing peri-Fused Macrocycles

Reagents and conditions: (a) O₂, hν; (b) Na₂S·9H₂O, DMF, 80 °C.

Chart 41. Miscellaneous Heteroatom-Bridged Cyclophanes