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Review
. 2008 Feb 1;3(2):164-94.
doi: 10.1002/asia.200700247.

Metal vinylidenes as catalytic species in organic reactions

Barry M Trost  1 , Andrew McClory
Affiliations
Review

Metal vinylidenes as catalytic species in organic reactions

Barry M Trost et al. Chem Asian J. .

Abstract

Organic vinylidene species have found limited use in organic synthesis owing to their inaccessibility. In contrast, metal vinylidenes are much more stable and may be readily accessed through transition-metal activation of terminal alkynes. These electrophilic species may be trapped by a number of nucleophiles. Additionally, metal vinylidenes can participate in pericyclic reactions and processes that involve migration of a metal ligand to the vinylidene species. This Focus Review addresses the reactions and applications of metal vinylidenes in organic synthesis.

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Figures

Figure 1
Figure 1
Ruthenium Catalysts for Anti-Markovnikov Alkyne Hydration.
Scheme 1
Scheme 1
Terminal Alkyne and the Corresponding Vinylidene
Scheme 2
Scheme 2
Synthetic Use of an Organic Vinylidene: Dreiding’s Synthesis of (+/−)-Isoptychanolide. FVT=flash vacuum thermolysis.
Scheme 3
Scheme 3
Formation of Metal Vinylidenes from Terminal Alkynes
Scheme 4
Scheme 4
Mechanisms of Metal Vinylidene Formation
Scheme 5
Scheme 5
Nucleophilic Addition to Metal Vinylidenes: Fischer Carbene Formation
Scheme 6
Scheme 6
Vinylcarbamates from Terminal Alkynes, Secondary Amines, and Carbon Dioxide
Scheme 7
Scheme 7
Mechanism of Vinylcarbamate Formation
Scheme 8
Scheme 8
Synthesis of Vinylcarbamates: Scope of Alkynes and Secondary Amines. dppe=bis(diphenylphosphino)ethane, nbd=norbornadiene, THF=tetrahydrofuran.
Scheme 9
Scheme 9
Formation of Enol Esters from Carboxylic Acids and Alkynes
Scheme 10
Scheme 10
Mechanism of Enol Ester Formation
Scheme 11
Scheme 11
Ruthenium-Catalyzed Formation of Enol Esters: Scope of Alkynes. dppb=bis(diphenylphosphino)butane.
Scheme 12
Scheme 12
Dixneuf’s Isomerization of Propargyl Alcohols to Enals. dppe=bis(diphenylphosphino)ethane, TsOH=p-toluenesulfonic acid.
Scheme 13
Scheme 13
Valerga’s Cyclization of α,ω-Alkynoic Acids
Scheme 14
Scheme 14
Ruthenium-Catalyzed Reconstitutive Condensation. Cp=η5-cyclopentadienyl.
Scheme 15
Scheme 15
Proposed Mechanism of Ruthenium-Catalyzed Reconstitutive Condensation
Scheme 16
Scheme 16
Trost’s Synthesis of a Functionalized Steroid Side Chain. Cp=η5-cyclopentadienyl., DMF=N,N-dimethylformamide, LDA=lithium diisopropylamide, THF=tetrahydrofuran.
Scheme 17
Scheme 17
Trost’s Synthesis of Rosefuran. Cp=η5-cyclopentadienyl., DMSO=dimethyl sulfoxide, NMO=N-methylmorpholine-N-oxide, TsOH=p-toluenesulfonic acid.
Scheme 18
Scheme 18
Trost’s Tandem Cyclization-Reconstitutive Condensation. Cp=η5-cyclopentadienyl.
Scheme 19
Scheme 19
Mechanism of Trost’s Tandem Cyclization-Reconstitutive Condensation. Cp=η5-cyclopentadienyl.
Scheme 20
Scheme 20
Trost’s Synthesis of The Spiroketal Subunit of (−)-Calyculin A. Cp=η5-cyclopentadienyl, (DHQD)PHN=dihydroquinidine 9-O-(9′-phenanthryl) ether, DIBALH=diisobutylaluminum hydride, PDC=pyridinium dichromate, TFA=trifluoroacetic acid, TsOH=p-toluenesulfonic acid.
Scheme 21
Scheme 21
McDonald’s Seminal Alkynol Cycloisomerization Reaction
Scheme 22
Scheme 22
Mechanism of Molybdenum-Catalyzed Alkynol Cycloisomerization
Scheme 23
Scheme 23
McDonald’s Syntheses of Stavudine and Cordycepin. DCE=1,2-dichloroethane, DIPT=diisopropyltartrate, M. S.=molecular sieves, NMO=N-methylmorpholine-N-oxide, THF=tetrahydrofuran, TMSOTf=trimethylsilyl trifluoromethanesulfonate.
Scheme 24
Scheme 24
McDonald’s Syntheses of 3-Aminonucleosides
Scheme 25
Scheme 25
McDonald’s Retrosynthetic Analysis of Digitoxin
Scheme 26
Scheme 26
McDonald’s Iterative Cycloisomerization Approach to Digitoxin. DIBALH=diisobutylaluminum hydride, DIPT=diisopropyltartrate, TBAF=tetrabutylammonium fluoride, TBSCl=tert-butyldimethylsilyl chloride, THF=tetrahydrofuran.
Scheme 27
Scheme 27
McDonald’s Syntheses of (L)-Vancosamine and (D)-Desosamine Glycals. DABCO=1,4-diazabicyclo[2.2.2]octane, THF=tetrahydrofuran.
Scheme 28
Scheme 28
McDonald’s Formation of α-Stannyl Vinyl Ethers from Alkynols. THF=tetrahydrofuran.
Scheme 29
Scheme 29
Ruthenium-Catalyzed Oxidative Cyclization of Homopropargyl Alcohols. COD=1,5-cyclooctadiene, Cp=η5-cyclopentadienyl, DMF=N,N-dimethylformamide.
Scheme 30
Scheme 30
Oxidative Cyclization vs. Cycloisomerization of Bis-homopropargyl Alcohols. Cp=η5-cyclopentadienyl, DMF=N,N-dimethylformamide.
Scheme 31
Scheme 31
Proposed Mechanism of Ruthenium-Catalyzed Oxidative Cyclization and Cycloisomerization
Scheme 32
Scheme 32
Trost’s Iterative Approach to Trans-Fused Polycyclic Ethers. BnBr=benzyl bromide, Cp=η5-cyclopentadienyl, DBU=1,8-diazabicyclo[5.4.0]undec-7-ene, DMDO=dimethyl dioxirane, DMF=N,N-dimethylformamide, PCC=pyridinium chlorochromate, THF=tetrahydrofuran, TsOH=p-toluenesulfonic acid.
Scheme 33
Scheme 33
Rhodium-Catalyzed Cycloisomerization of Homo- and Bis-homopropargyl Alcohols. COD=1,5-cyclooctadiene, DMF=N,N-dimethylformamide.
Scheme 34
Scheme 34
Wakatsuki’s Anti-Markovnikov Hydration of Terminal Acetylenes
Scheme 35
Scheme 35
Mechanism of Anti-Markovnikov Alkyne Hydration
Scheme 36
Scheme 36
Wakatsuki’s Isomerization of Propargyl Alcohols. Cp=η5-cyclopentadienyl.
Scheme 37
Scheme 37
Proposed Mechanism of Propargyl Alcohol Isomerization. Cp=η5-cyclopentadienyl.
Scheme 38
Scheme 38
Lee’s Hydrative Cyclization of 1,5-Enynes. dppm=bis(diphenylphosphino)methane.
Scheme 39
Scheme 39
Proposed Mechanism for Lee’s Hydrative Cyclization of 1,5-Enynes. dppm=bis(diphenylphosphino)methane.
Scheme 40
Scheme 40
Formation of Furans from Epoxyalkynes. DCE=1,2-dichloroethane, Tp=tris(pyrazolyl)borate.
Scheme 41
Scheme 41
Mechanism of Furan Formation from Epoxyalkynes.
Scheme 42
Scheme 42
Liu’s Syntheses of 2-Naphthols and 1-Alkylidene-2-Indanones. Tp=tris(pyrazolyl)borate.
Scheme 43
Scheme 43
Mechanism of 2-Naphthol and 1-Alkylidene-2-Indanone Formation. Tp=tris(pyrazolyl)borate.
Scheme 44
Scheme 44
Liu’s Formation of 1-Iodo-2-Naphthols. Tp=tris(pyrazolyl)borate.
Scheme 45
Scheme 45
Uemura’s Synthesis and Diels-Alder Reaction of Pyranylidenes. DMAD= dimethylacetylene dicarboxylate, THF=tetrahydrofuran.
Scheme 46
Scheme 46
Iwasawa’s Synthesis and Diels-Alder Reaction of Benzopyranylidenes. THF=tetrahydrofuran.
Scheme 47
Scheme 47
Uemura’s Catalytic Synthesis of Phenols from cis-1-Acyl-2-ethynylcyclopropanes. THF=tetrahydrofuran.
Scheme 48
Scheme 48
Mechanism of Phenol Formation from cis-1-Acyl-2-ethynylcyclopropanes. THF=tetrahydrofuran.
Scheme 49
Scheme 49
Cycloisomerization of Homopropargyl Thiols. DBU=1,8-diazabicyclo[5.4.0]undec-7-ene, THF=tetrahydrofuran.
Scheme 50
Scheme 50
Watanabe’s Synthesis of an Enamide from Acetanilide and 1-Octyne
Scheme 51
Scheme 51
Gooβen’s Synthesis of Enamides from Amides and Alkynes. COD=1,5-cyclooctadiene, DMAP=4-dimethylaminopyridine.
Scheme 52
Scheme 52
Fukumoto’s Nitrile Synthesis from N,N-Dimethylhydrazine and Alkynes. Tp=tris(pyrazolyl)borate.
Scheme 53
Scheme 53
Proposed Mechanism of Fukumoto’s Nitrile Synthesis. Tp=tris(pyrazolyl)borate.
Scheme 54
Scheme 54
McDonald’s Cycloisomerization of Homo- and Bis-homopropargyl Amines. THF=tetrahydrofuran.
Scheme 55
Scheme 55
Trost’s Cycloisomerization of o-Ethynylanilines to Indoles
Scheme 56
Scheme 56
Jun’s Chelation-Assisted Hydrative Dimerization of Terminal Alkynes. THF=tetrahydrofuran.
Scheme 57
Scheme 57
Mechanism of Jun’s Chelation-Assisted Hydrative Dimerization of Terminal Alkynes
Scheme 58
Scheme 58
Hydrophosphination of Propargyl Alcohols. COD=1,5-cyclooctadiene, Cp=η5-cyclopentadienyl.
Scheme 59
Scheme 59
Cyclization of Homo- and Bis-homopropargyl β-Dicarbonyl Compounds
Scheme 60
Scheme 60
Mechanism of McDonald’s Homopropargyl β-Dicarbonyl Cycloisomerization
Scheme 61
Scheme 61
Iwasawa’s Cycloisomerization of Homo- and Bis-homopropargyl Silyl Enol Ethers. THF=tetrahydrofuran.
Scheme 62
Scheme 62
Iwasawa’s Cyclopentene Annulation Method. DABCO=1,4-diazabicyclo[2.2.2]octane, TBSOTf= tert-butyldimethylsilyl trifluoromethanesulfonate, THF=tetrahydrofuran.
Scheme 63
Scheme 63
Iwasawa’s Cyclopentene Annulation Method: Iodine Migration. THF=tetrahydrofuran.
Scheme 64
Scheme 64
Lee’s N-Propargyl Enamine Cycloisomerization. DABCO=1,4-diazabicyclo[2.2.2]octane, DMF= N,N-dimethylformamide.
Scheme 65
Scheme 65
Proposed Mechanism of N-Propargyl Enamine Cycloisomerization
Scheme 66
Scheme 66
Merlic’s Dienyne Cycloisomerization
Scheme 67
Scheme 67
Plausible Mechanism for Dienyne Cycloisomerization
Scheme 68
Scheme 68
Scott’s Naphthonannulation Procedure. DCE=1,2-dichloroethane, TBAF=tetrabutylammonium fluoride.
Scheme 69
Scheme 69
Iwasawa’s Dienyne Cycloisomerization. THF=tetrahydrofuran.
Scheme 70
Scheme 70
Akiyama’s Cycloisomerization of Alkynyl Imines. NMO= N-methylmorpholine N-oxide, THF=tetrahydrofuran.
Scheme 71
Scheme 71
Liu’s Electrocyclization and Halide Migration. Tp=tris(pyrazolyl)borate.
Scheme 72
Scheme 72
Mechanism of Liu’s Electrocyclization and Halide Migration. Tp=tris(pyrazolyl)borate.
Scheme 73
Scheme 73
Liu’s Formation of Substituted Benzenes and 2-Vinyl 1H-Indenes. Tp=tris(pyrazolyl)borate.
Scheme 74
Scheme 74
Mechanism of Liu’s Substituted Benzene Synthesis. Tp=tris(pyrazolyl)borate.
Scheme 75
Scheme 75
Mechanism of Liu’s 2-Vinyl 1H-Indene Synthesis. Tp=tris(pyrazolyl)borate.
Scheme 76
Scheme 76
Murakami’s Intermolecular Alkene-Alkyne Coupling. Cp=η5-Cyclopentadienyl.
Scheme 77
Scheme 77
Mechanism of Intermolecular Enyne Coupling. Cp=η5-Cyclopentadienyl.
Scheme 78
Scheme 78
Murakami’s Tandem Enyne Coupling-Electrocyclization. Cp=η5-Cyclopentadienyl.
Scheme 79
Scheme 79
Murakami’s Alkenylation of Pyridine. Cp=η5-Cyclopentadienyl.
Scheme 80
Scheme 80
Rhodium-Catalyzed Enyne Cycloisomerization. COD=1,5-cyclooctadiene, DMF= N,N-dimethylformamide.
Scheme 81
Scheme 81
Mechanism of Rhodium-Catalyzed Enyne Cycloisomerization. COD=1,5-cyclooctadiene.
Scheme 82
Scheme 82
Lee’s Tandem Cyclization of 1,6-Enyne Systems. COD=1,5-cyclooctadiene, DMF= N,N-Dimethylformamide.
Scheme 83
Scheme 83
Mechanism of the Tandem 1,6-Enyne Cyclization. COD=1,5-cyclooctadiene.
Scheme 84
Scheme 84
Buono’s Palladium-Catalyzed [2+1] Cycloaddition
Scheme 85
Scheme 85
Mechanism of Buono’s Palladium-Catalyzed [2+1] Cycloaddition
Scheme 86
Scheme 86
Tagliatesta’s Synthesis of 1-Arylnaphthalenes
Scheme 87
Scheme 87
Mechanism of 1-Arylnaphthalene Formation from Arylacetylenes
Scheme 88
Scheme 88
Liu’s Cyclopentadiene Synthesis. Tp= tris(pyrazolyl)borate.
Scheme 89
Scheme 89
Mechanism of Cyclopentadiene Formation. Tp= tris(pyrazolyl)borate.
Scheme 90
Scheme 90
Finn’s Stoichiometric Metal-Mediated Cycloaromatization. Cp=η5-Cyclopentadienyl.
Scheme 91
Scheme 91
Uemura’s Rhodium-Catalyzed Cycloaromatization: 1,5-Hydrogen Migration
Scheme 92
Scheme 92
Mechanism of Rhodium-Catalyzed Cycloaromatization: 1,5-Hydrogen Migration
Scheme 93
Scheme 93
Uemura’s Rhodium-Catalyzed Cycloaromatization: 1,6-Hydrogen Migration
Scheme 94
Scheme 94
Mechanism of Rhodium-Catalyzed Cycloaromatization: 1,6-Hydrogen Migration
Scheme 95
Scheme 95
Yamazaki’s Dimerization of t-Butylacetylene
Scheme 96
Scheme 96
Catalytic Cycle for Yamazaki’s Dimerization of t-Butylacetylene
Scheme 97
Scheme 97
Bianchini’s Dimerization of Trimethylsilylacetylene and Phenylacetylene. THF=tetrahydrofuran.
Scheme 98
Scheme 98
Yi’s Stereoselective Dimerization of Phenylacetylene: Ligand Effect. Cp*=1,2,3,4,5-η5-pentamethylcyclopentadienyl, THF=tetrahydrofuran.
Scheme 99
Scheme 99
Alkyne Dimerization: Rationale for Product Formation. Cp*=1,2,3,4,5-η5-pentamethylcyclopentadienyl.
Scheme 100
Scheme 100
Hidai’s Head-to-Head Dimerization of Aliphatic Terminal Alkynes. Cp*=1,2,3,4,5-η5-pentamethylcyclopentadienyl.
Scheme 101
Scheme 101
Bianchini’s Dimerization of Aromatic and Aliphatic Terminal Alkynes
Scheme 102
Scheme 102
Katayama’s Cross-Dimerization of Arylacetylenes with Silylacetylenes
Scheme 103
Scheme 103
Lee’s Carboxylative Cyclization of 1,6-Diynes
Scheme 104
Scheme 104
Mechanism of the 1,6-Diyne Carboxylative Cyclization
Scheme 105
Scheme 105
Lee’s Arylative Cyclization of 1,5-Enynes. COD=1,5-cyclooctadiene.
Scheme 106
Scheme 106
Mechanism of 1,5-Enyne Arylative Cyclization. COD=1,5-cyclooctadiene.
Scheme 107
Scheme 107
Miyaura’s Z-Selective Hydroboration of Terminal Alkynes. COD=1,5-cyclooctadiene.
Scheme 108
Scheme 108
Z-Selective Hydroboration of Terminal Alkynes: Mechanistic Rationale. COD=1,5-cyclooctadiene.
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