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. 2017 Feb 3;7(2):1340-1360.
doi: 10.1021/acscatal.6b03210. Epub 2017 Jan 6.

"Cut and Sew" Transformations via Transition-Metal-Catalyzed Carbon-Carbon Bond Activation

Peng-Hao Chen  1 , Brent A Billett  2 , Tatsuhiro Tsukamoto  2 , Guangbin Dong  2
Affiliations

"Cut and Sew" Transformations via Transition-Metal-Catalyzed Carbon-Carbon Bond Activation

Peng-Hao Chen et al. ACS Catal. .

Abstract

The transition metal-catalyzed "cut and sew" transformation has recently emerged as a useful strategy for preparing complex molecular structures. After oxidative addition of a transition metal into a carbon-carbon bond, the resulting two carbon termini can be both functionalized in one step via the following migratory insertion and reductive elimination with unsaturated units, such as alkenes, alkynes, allenes, CO and polar multiple bonds. Three- or four-membered rings are often employed as reaction partners due to their high ring strains. The participation of non-strained structures generally relies on cleavage of a polar carbon-CN bond or assistance of a directing group.

Keywords: carbon–carbon activation; cut and sew; oxidative addition; reductive elimination; transition-metal catalysis.

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Figures

Scheme 1
Scheme 1
“Cut and sew” transformations
Scheme 2
Scheme 2
Reaction patterns for ACPs
Scheme 3
Scheme 3
Substitution-controlled [3+2] cycloaddition of ACPs
Scheme 4
Scheme 4
Pd-catalyzed intramolecular cycloaddition between ACPs and alkenes or alkynes
Scheme 5
Scheme 5
Heteroatom-assisted intramolecular cycloaddition between simple MCPs and alkenes
Scheme 6
Scheme 6
Stereoselective intramolecular [3+2] reactions of ACPs with tethered alkynes
Scheme 7
Scheme 7
Proposed mechanism for the intramolecular [3+2] reactions of ACPs with tethered alkynes
Scheme 8
Scheme 8
Ni-catalyzed intermolecular cycloaddition with cyclopropylideneacetates
Scheme 9
Scheme 9
Ni-catalyzed intermolecular [3+2+2] cycloaddition with two different alkyne components
Scheme 10
Scheme 10
Ni-catalyzed [3+2+2] cycloadditions between alkyne-tethered ACPs and alkenes
Scheme 11
Scheme 11
Ni-catalyzed cycloaddition of ACPs and alkynes via proximal C–C cleavage
Scheme 12
Scheme 12
Alkene-assisted intermolecular [3+2] cycloaddition of ACPs and alkenes
Scheme 13
Scheme 13
Rh-catalyzed intramolecular [3+2+1] cycloaddition of simple cyclopropanes with alkynes
Scheme 14
Scheme 14
Ni-catalyzed intermolecular [3+2] cycloaddition of acyl cyclopropanes with enones
Scheme 15
Scheme 15
Ni-catalyzed intermolecular [3+2] cycloaddition of cyclopropyl ketones with alkynes
Scheme 16
Scheme 16
Urea-directed Rh-catalyzed intramolecular [3+2+1] cycloaddition of cyclopropyl amides with alkynes
Scheme 17
Scheme 17
Cationic rhodium-catalyzed for [3+2+1] cycloaddition of cyclopropyl amides
Scheme 18
Scheme 18
Directed intramolecular [3+2+1] cycloaddition of aminomethylcyclopropanes
Scheme 19
Scheme 19
General types of VCPs
Scheme 20
Scheme 20
Two mechanistic pathways for VCPs acting as a five-carbon component
Scheme 21
Scheme 21
VCPs serving as 1,3-dipoles
Scheme 22
Scheme 22
Rh-catalyzed [3+2] cycloaddition of 2-ene-VCPs
Scheme 23
Scheme 23
Rh-catalyzed [3+2] cycloaddition of 1-substituted-VCPs.
Scheme 24
Scheme 24
Reaction mechanism of the [3+2] cycloaddition of 1-substituted-VCPs
Scheme 25
Scheme 25
Asymmetric [3+2] cycloaddition of 1-substituted-VCPs
Scheme 26
Scheme 26
Carbonylative [3+2+1] cycloadditions of 1-substituted-VCPs.
Scheme 27
Scheme 27
Carbonylative [5 + 1]/[2 + 2 + 1] or [3+2+1] cycloadditions of 1-substituted-VCPs
Scheme 28
Scheme 28
[3+2] cycloaddition of α-substituted-VCPs
Scheme 29
Scheme 29
Ni-catalyzed intermolecular [3+2] cycloaddition between VCPs and allenes
Scheme 30
Scheme 30
Cyclopropenone-mediated cycloaddition
Scheme 31
Scheme 31
Intermolecular [3+2] cycloaddition between cyclopropenones and alkynes
Scheme 32
Scheme 32
Intramolecular [3+2] cycloaddition of cyclopropenes
Scheme 33
Scheme 33
Carboacylation with the styrene-tethered cyclobutanones
Scheme 34
Scheme 34
Proposed pathway for the Rh-catalyzed carboacylation of the styrene-tethered cyclobutanones
Scheme 35
Scheme 35
Enantioselective carboacylation of the styrene-tethered cyclobutanones
Scheme 36
Scheme 36
Competing decarbonylation pathway
Scheme 37
Scheme 37
A temporary DG-based strategy for the “cut and sew” reaction with cyclobutanones and olefins
Scheme 38
Scheme 38
[4+1] cycloaddition of cyclobutanones and allenes
Scheme 39
Scheme 39
Proposed mechanism of the [4+1] cycloaddition of cyclobutanones and allenes
Scheme 40
Scheme 40
Rhodium-catalyzed [4+2-1] cycloaddition
Scheme 41
Scheme 41
Synthesis of tolciclate
Scheme 42
Scheme 42
Asymmetric carbonyl insertion to cyclobutanone
Scheme 43
Scheme 43
Proposed catalytic cycle of the Rh-catalyzed carbonyl-cyclobutanone coupling
Scheme 44
Scheme 44
Quinone synthesis from C–C activation of cyclobutenediones
Scheme 45
Scheme 45
Phenol synthesis from C–C activation of cyclobutenones
Scheme 46
Scheme 46
Alkynyl boronate insertion into cyclobutenones
Scheme 47
Scheme 47
Norbornene insertion into cyclobutenediones
Scheme 48
Scheme 48
Rh-catalyzed norbornene-cyclobutenone coupling
Scheme 49
Scheme 49
Cyclobutenone dimerization
Scheme 50
Scheme 50
Proposed reaction pathway of the norbornene-cyclobutenone coupling
Scheme 51
Scheme 51
Coupling of electron-deficient olefins with cyclobutenones
Scheme 52
Scheme 52
Intramolecular decarbonylative alkene insertion with cyclobutenediones
Scheme 53
Scheme 53
Selective proximal C1–C2 cleavage of benzocyclobutenones and tethered olefin insertion
Scheme 54
Scheme 54
Effect of ZnCl2 on challenging olefin substrates
Scheme 55
Scheme 55
Indirect proximal C1–C2 activation through decarbonylative CO migration
Scheme 56
Scheme 56
Enantioselective “cut and sew” transformation with benzocyclobutenones
Scheme 57
Scheme 57
Reductive dearomatization of the tricyclic products
Scheme 58
Scheme 58
Coupling of trisubstituted olefins and its application in the total synthesis of cycloinumakiol
Scheme 59
Scheme 59
Alkyne insertion into benzocyclobutenones
Scheme 60
Scheme 60
A divergent approach to access fused naphthols and indenes
Scheme 61
Scheme 61
Enantioselective C=N bond insertion into benzocyclobutenones
Scheme 62
Scheme 62
Diastereoselective hydrogenation of the fused scaffold
Scheme 63
Scheme 63
Intermolecular coupling of benzocyclobutenones with 1,3-dienes and acetylenes
Scheme 64
Scheme 64
Rh-catalyzed coupling between methylidenecyclobutenes and alkynes
Scheme 65
Scheme 65
Ni-catalyzed insertion of alkynes, CO and isocyanides with biphenylenes
Scheme 66
Scheme 66
Using a Ni catalyst with a P,N-ligand
Scheme 67
Scheme 67
Formation of axial chirality via the “cut and sew” reaction with biphenylenes
Scheme 68
Scheme 68
Coupling of biphenylenes with nitriles to form phenanthridines
Scheme 69
Scheme 69
General mechanism for the TM-catalyzed “cut and sew” reactions via C–CN bond activation
Scheme 70
Scheme 70
8-Quinoline-directed intramolecular carboacylation of tethered alkenes
Scheme 71
Scheme 71
Proposed reaction mechanism for the 8-quinoline-directed intramolecular carboacylation of tethered alkenes
Scheme 72
Scheme 72
Directed intermolecular carboacylation of norbornene derivatives
Scheme 73
Scheme 73
Directed selective C–C activation of isatins followed by decarbonylative coupling with alkynes
Scheme 74
Scheme 74
C–C activation of isatins followed by decarbonylation and coupling with isocyanates
Scheme 75
Scheme 75
Proposed mechanism for the double-decarbonylative coupling reaction
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