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Review
. 2008 Jan;108(1):264-87.
doi: 10.1021/cr078199m. Epub 2007 Dec 21.

Lamellarins and related pyrrole-derived alkaloids from marine organisms

Hui Fan  1 , Jiangnan Peng, Mark T Hamann, Jin-Feng Hu
Affiliations
Review

Lamellarins and related pyrrole-derived alkaloids from marine organisms

Hui Fan et al. Chem Rev. 2008 Jan.

Erratum in

  • Chem Rev. 2010 Jun 9;110(6):3850
No abstract available

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Figures

Figure 1
Figure 1
Structure of lamellarins 1a–c.
Figure 2
Figure 2
Structures of lamellarin-related pyrrole-derived alkaloids.
Figure 3
Figure 3
Possible biogenetic pathways for several apparently DOPA-derived alkaloids from marine ascidians. (Reprinted with permission from ref . Copyright 1997 American Chemical Society.)
Figure 4
Figure 4
Possible biogenetic relationship between the lamellarins, polycitone A (58) and polycitrins A (60) and B (61). (Reprinted with permission from ref . Copyright 1994 American Chemical Society.)
Scheme 1
Scheme 1
Synthesis of Lamellarins D (35) and H (37)a a Reagents and conditions: (i) LDA, THF, 79, 63%; (ii) BrCH2CO2Et; (iii) cat. HCl, MeOH; (iv) Et3N, CH2Cl2, 34% (3 steps); (v) H2, Pd(OH)2/C, EtOAC, 82%; (vi) BBr3, CH2Cl2, 68%. (Reprinted with permission from ref . Copyright 1997 Elsevier B.V.)
Scheme 2
Scheme 2
Synthesis of Lamellarin D (35)a a Reagents and conditions: (i) (1) 85, NaH, DMF, (2) PdCl2(pph3)2, PPh3, K2CO3; (ii) NBS, THF; (iii) 88, Pd(PPh3)4, Na2CO3, DMF; (iv) i-PrBr, K2CO3, DMF; (v) NBS, THF; (vi) 92, Pd(PPh3)4, K3PO4, DMF; (vii) DDQ, CHCl3, MW; (viii) AlCl3, CH2Cl2; (ix) NaH, THF. (Reprinted with permission from ref . Copyright 2005 American Chemical Society.)
Scheme 3
Scheme 3
Synthesis of Lamellarins D (35), L (15), and N (40)a a Reagents and conditions: (i) 97 or 98 (1.0 equiv), Pd(PPh3)4 (2 mol %), THF, reflux, 4 h (99, 76%; 100, 77%); (ii) (1)101 (2.0 equiv), Pd(PPh3)4 (8 mol %), THF, reflux, 18 h, (2) concd HCl, MeOH, reflux 1 h (102, 98%; 103, 95%); (iii) (1) 40% KOH–EtOH (1/1), reflux, 3 h, (2) cat. p-TsOH, CH2Cl2, reflux, 1 h (104, 90%; 105, 91%); (iv) Cu2O, quinoline, 220 °C, 7 min (106, 94%; 107, 99%); (v) Phl(OCOCF3)2, BF3·OEt2, CH2Cl2, −40 °C, 1.5 h (108, 88%; 109, 90%); (vi) Pd(OAc)2 (1.1 equiv), CH3CN, reflux, 12 h (110, 65%; 106, 14%; 109, 65%; 107, 15%); (vii) DDQ (1.5 equiv), toluene, reflux, 18 h (110, 97%; 111, 96%); (viii) BCl3, CH2Cl2, −78 °C, 0.5 h, then rt, 3 h (35, quant; 15, 98%; 40, 88%). (Reprinted with permission from ref . Copyright 2006 Elsevier B.V.)
Scheme 4
Scheme 4
Synthesis of Lamellarin H (37), Lamellarin α (45), and Lamellarin α 13,20-Disulfate (47)a a Reagents and conditions: (i) i-PrBr, K2CO3, DMF, rt, 48 h; (ii) CBr4, Zn, PPh3, CH2Cl2, 0–25 °C, 4 h; (iii) n-BuLi, THF, −78 to −25 °C, 2 h; (iv) AgOCOCF3, I2, CH2Cl2, reflux, 12 h; (v) Pd(PPh3)4, CuI, NEt3, 45 °C, 5 h; (vi) MCPBA, KHCO3, CH2Cl2, rt,1 h; (vii) NH3, CH2Cl2/MeOH (1:1), rt, 2 h; (viii) ICH2COOH, DCC, DMAP, CH2Cl2, rt, 5 h; (ix) ClCH2CH2Cl, rt, 24 h; (x) Hunig’s base, reflux, 30 h; (xi) DDQ, CH2Cl2/EtOH (1:1), reflux, 48 h; (xii) BCl3, CH2Cl2, 0 °C, 6 h; (xiii) DMF–SO3, DMF/pyridine (4:1), 65 °C, 2 h; (xiv) BBr3, CHCl3, 55 °C, 24 h. (Reprinted with permission from ref . Copyright 2002 Elsevier B.V.)
Scheme 5
Scheme 5
Synthesis of Lamellarins K (12) and L (15)a a Reagents and conditions: (i) NaHCO3, 125, CH3CN, reflux, 70% (126), 70% (127); (ii) H2, Pd/C, EtOAC; (iii) NaH, THF, 93% (12, over 2 steps), 87% (15, over 2 steps). (Reprinted with permission from ref . Copyright 2004 by John Wiley & Sons, Inc.)
Scheme 6
Scheme 6
Synthesis of Lamellarin U (22) and Lamellarin L (15)a a Reagents and conditions: (i) DEAD, PPh3, DIEA, THF, 0 °C, 10 min, rt, 3 h, loading of Merrifield resin = 0.68 mmol/g; (ii) 2-ethynyl-5-isopropoxy-4-methoxy-benzaldehyde (3 equiv), CuI (0.6 equiv), Pd [(Ph3)2Cl2] (0.3 equiv), THF–Et3N (3:1), N2, 20 h; (iii) mCPBA (6 equiv), NaHCO3 (12 equiv), CH2Cl2, 0–20 °C, 15 h; (iv) 2 M KOH, THF–MeOH, rt, 5 h; (v) ICH2CO2H (10 equiv), DMAP (15%), DIP (10 equiv), DMF, rt, 12 h; (vi) 3,4-dihydro-6,7-dimethoxyisoquinoline (6 equiv), CH2ClCH2Cl, rt, 24 h; (vii) DIEA (7 equiv), 83 °C, 24 h; (viii) AlCl3 (15 equiv), CH2Cl2, rt, 12 h. (Reprinted with permission from ref . Copyright 2003 American Chemical Society.)
Scheme 7
Scheme 7
Convergent Synthesis of Lamellarins O (52) and Q (54) and Lukianol A (56)a a Reagents and conditions: (i) NBS (3 equiv), THF, −78 °C, 1 h then 20 °C for 4 h; (ii) PhLi (1 equiv), −78 °C, 0.16 h then ClCO2Me (1.05 equiv), −78 to 20 °C, 1 h; (iii) Pd(PPh3)2Cl2 (10 mol %), 1,4,-dioxane, 101 °C, 14 h; (iv) Bu4NF (10 mol % excess), THF, 20 °C, 1 h then 0.5 M aq.HCl; (v) p-MeOC6H4COCH2Br (3 equiv.), K2CO3 (5 equiv.), Bu4NCl (20 mol %), THF, 66 °C, 7 h; (vi) Pd(PPh3)4 (5 mol %), satd aq. Na2CO3 (6 equiv), DMF, 153 °C, 23 h; (vii) see ref . (Reprinted with permission from ref . Copyright Royal Society of Chemisty 1997.)
Scheme 8
Scheme 8
Synthesis of Lukianol A (56)a a Reagents and conditions: (i) H2O2, NaOH, EtOH/H2O, 0 °C, 98%; (ii) (1) BF3·Et2O, Et2O, reflux; (2) NH2OH·HCl, pyridine, EtOH, reflux, 67% (over 2 steps); (iii) H2 (1 atm), Pd (5%)/C, THF, 94%, (Z):(E) = 1:1; (iv) ClOCCO2Me, pyridine, THF, 73%, (Z):(E) = 2.5:1; v, Ti–graphite (TiCl3:C8K = 1:2), DME, reflux, 52%; (vi) p-MeO–C6H4COCH2Br, K2CO3, acetone, reflux, 91%; (vii) (1) KO–tBu, H2O, Et2O, 0 °C; (2) Ac2O, NaOAC, reflux, 59% (over 2 steps); (viii) BBr3, CH2Cl2, −78 °C, 99%. (Reprinted with permission from ref . Copyright 1995 American Chemical Society.)
Scheme 9
Scheme 9
Biomimetic Total Synthesis of Polycitrin A (60)a a Reagents and conditions: (i) (1) THF, n-BuLi, −78 °C, (2) 0.5 equiv, I2, −78 to 25 °C, (3) NH3, TiCl4, 72%; (ii) NaOCl,95%; (iii) NaHSO3; (iv) (1) KOH, (2) HCl, 75%; (v) BBr3, 78%; (vi) Br2, AcOH,83%; (vii) tyramine, diisopropylethylamine, PhOH (melt), 160 °C, 78%. (Reprinted with permission from ref . Copyright 1995 Elsevier B.V.)
Scheme 10
Scheme 10
Total Synthesis of Polycitrin B (61)a a Reagents and conditions: (i) Br2,FeBr2, 80%; (ii) MeONa, MeOH, (CO2Me)2, 99%; (iii) (CF3SO2)2O, iPr2NEt,CH2Cl2, 84%; (iv) 169, Pd2dba3, Ph3P,DMF, 81%; (v) Me3SiCl, NaI, MeCN, 92%; (vi) NaOH, H2O, MeOH, 77%; (vii) Br2,AcOH, 89%; (viii) tyramine, iPr2NEt, phenol, molecular sieves, 140 °C. (Reprinted with permission from ref . Copyright 2000 Elsevier B.V.)
Scheme 11
Scheme 11
Synthesis of Ningalin A (73)a a Reagents and conditions: (i) Bu3SnCCSnBu3,(Ph3P)4Pd, 79%; (ii) 176, 87%; (iii) Zn, HOAC, 63%; (iv) HCl·EtOAc, 94%; (v) DBU, 100%; (vi) BBr3, 96%. (Reprinted with permission from ref . Copyright 1999 American Chemical Society.)
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