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. 2015 Sep 9;115(17):9028-72.
doi: 10.1021/cr500691k. Epub 2015 Apr 6.

Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity

Ruth Dorel  1 , Antonio M Echavarren  1   2
Affiliations

Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity

Ruth Dorel et al. Chem Rev. .
No abstract available

PubMed Disclaimer

Figures

Scheme 1
Scheme 1. Anti-Nucleophilic Attack to η2-[AuL]+-Activated Alkynes
Figure 1
Figure 1
Increase in electrophilicity with decreased donating ligand ability in gold(I) complexes.
Scheme 2
Scheme 2. Hydration and Acetalization of Alkynes with Ph3PAuMe and Protic Acids
Scheme 3
Scheme 3. Hydration of Alkynes with Low-Catalyst Loadings
Scheme 4
Scheme 4. Hydration of Haloalkynes
Scheme 5
Scheme 5. Acetalization of Alkynes
Scheme 6
Scheme 6. Bromo-Acetalization of Alkynes
Scheme 7
Scheme 7. Synthesis of Homoallylic Ketones by Nucleophilic Addition-Claisen Rearrangement
Scheme 8
Scheme 8. Synthesis of Furans by Cyclization of Alkynediols
Scheme 9
Scheme 9. Cyclization of Epoxy and Ketoalkynes
Scheme 10
Scheme 10. Synthesis of Furan Derivatives from Z-Enynols
Scheme 11
Scheme 11. Synthesis of Oxazocenones
Scheme 12
Scheme 12. Intramolecular Acetalization of Alkynes
Scheme 13
Scheme 13. Tandem Cycloisomerization/Hydroalkoxylation of Homopropargylic Alcohols
Scheme 14
Scheme 14. Synthesis of Bicyclo[3.2.0]heptenes by Intramolecular Addition to a Cyclopropyl Alkyne
Scheme 15
Scheme 15. Synthesis of 3-Alkoxyfurans from Acetal-Containing Propargylic Alcohols
Scheme 16
Scheme 16. Synthesis of Naphthol Derivatives from Diethynylketones
Scheme 17
Scheme 17. Synthesis of Tricyclic Spiroketones by Tandem Hydration/Conia-Ene/Aldol Condensation
Scheme 18
Scheme 18. Synthesis of Cyclopentenylketones from 2-Alkynyl-1,5-diketones
Scheme 19
Scheme 19. Catalyst-Dependent Synthesis of 1,3-Cyclohexadienes
Scheme 20
Scheme 20. Synthesis of Oxygen-Containing [3.3.2] Bicyclic Compounds by Cascade Sequences Involving Intramolecular Hydroalkoxylations
Scheme 21
Scheme 21. Enantioselective Synthesis of Spiroketals by Coupling of Alkynols, Anilines, and Glyoxylic Acid
Scheme 22
Scheme 22. Intramolecular Addtion of O-Nucleophiles to Alkynes
Scheme 23
Scheme 23. Synthesis of Dihydropyridones by Intramolecular Addition of Homorpropargylic Amides to Alkynes
Scheme 24
Scheme 24. Reaction of 1-Oxo-4-oxy-5-ynes with Alkenes To Form 9-Oxabicyclo[3.3.1]nona-4,7-dienes
Scheme 25
Scheme 25. Synthesis of (−)-atrop-Abyssomicin C
Scheme 26
Scheme 26. Synthesis of Bryostatin 16
Scheme 27
Scheme 27. Construction of the Spiroketal Fragments in the Total Synthesis of Okadic Acid
Scheme 28
Scheme 28. Synthesis of Neurymenolide A
Scheme 29
Scheme 29. Synthesis of Psymberin
Scheme 30
Scheme 30. Intermolecular Amination of Alkynes to Form Imines
Scheme 31
Scheme 31. Regioselective Hydroamination of Unsymmetrical Alkynes
Scheme 32
Scheme 32. Synthesis of Azaflavanones and Quinoline Derivatives
Scheme 33
Scheme 33. Enantioselective Hydroamination/Transfer Hydrogenation Synthesis of Secondary Amines
Scheme 34
Scheme 34. Synthesis of Polysubstituted Pyrroles from 2H-Azirines and Ynamides
Scheme 35
Scheme 35. Synthesis of 2,5- or 2,4-Disubstituted Pirroles from Aryl-Substituted N-Tosyl Alkynylaziridines
Scheme 36
Scheme 36. Synthesis of Substituted Pyrroles by an Intermolecular Hydroamination
Scheme 37
Scheme 37. Cyclization of o-Alkynylbenzyl Carbamates
Scheme 38
Scheme 38. Tandem hydroamination/Cyclization of Alkynyl Carbamates
Scheme 39
Scheme 39. Regiodivergent Cyclization of o-Ethynylarylureas
Scheme 40
Scheme 40. Synthesis of Aryl-Annulated Carbazoles by Hydroamination/Hydroarylation
Scheme 41
Scheme 41. Synthesis of (−)-Quinocarcin
Scheme 42
Scheme 42. Synthesis of (−)-Rhazinicine and (−)-Rhazinilam
Scheme 43
Scheme 43. Synthesis of Benzothiophenes by Cyclization of Aryl Thioethers
Scheme 44
Scheme 44. Synthesis of 3-Silylbenzothiophenes and O-Heterocyclic Boronic Acid Derivatives
Scheme 45
Scheme 45. Synthesis of Eight-Membered Cyclic Allenes
Scheme 46
Scheme 46. General Pathways for the Cycloisomerization of 1,6-Enynes
Scheme 47
Scheme 47. Single-Cleavage Rearrangement of 1,6-Enynes
Scheme 48
Scheme 48. Single-Cleavage Rearrangement of 1,6-Enynes with Electron-Donating Groups at the Alkene
Scheme 49
Scheme 49. Double-Cleavage Rearrangement of 1,6-Enynes with Alkyl-Substituted Alkynes
Scheme 50
Scheme 50. Endo-Type Single-Cleavage Rearrangement
Scheme 51
Scheme 51. Synthesis of Oxa- and Aza-Bicyclo[4.1.0]hept-4-enes by Cycloisomerization of 1,6-Enynes
Scheme 52
Scheme 52. Cycloisomerization Followed by a 1,2-Alkyl Carbocationic Shift
Scheme 53
Scheme 53. Polycyclization of Dienediynes To Form 5,7,6-Tricyclic Ring Systems
Scheme 54
Scheme 54. Single-Cleavage Rearrangement of 1,7-Enynes
Scheme 55
Scheme 55. Formation of 5-Membered Rings by Conia-Ene Cyclization
Scheme 56
Scheme 56. Exo-Cyclization of Silyl Enol Ethers with Alkynes
Scheme 57
Scheme 57. Synthesis of Benzoxocines by Cyclization of 1,7-Enynes
Scheme 58
Scheme 58. Formal [2 + 2] Intramolecular Cycloaddition Between Alkene and Alkyne
Scheme 59
Scheme 59. Synthesis of a 10-Membered-Ring Compound by Cycloisomerization of a 1,9-Enyne
Scheme 60
Scheme 60. Macrocyclization of 1,n-Enynes
Scheme 61
Scheme 61. Synthesis of Naphthalenes by endo-dig Cyclization of 1,5-Enynes
Scheme 62
Scheme 62. Enantioselective Cycloisomerization of 2-Alkynylstyrenes
Scheme 63
Scheme 63. Synthesis of Azaanthraquinones from N-Propargylaminoquinones
Scheme 64
Scheme 64. Synthesis of Bicyclo[3.1.0]hexenes by endo-dig Cycloisomerization of 1,5-Enynes
Scheme 65
Scheme 65. endo-dig Cycloisomerization of 1,5-Enynes Followed by Ring Expansion and C–H Insertion
Scheme 66
Scheme 66. Enantioselective Ring-Expanding Cycloisomerization of Cyclopropylidene 1,5-Enynes
Scheme 67
Scheme 67. General Pathways for the Cycloisomerization of 3-Hydroxylated-1,5-Enynes
Scheme 68
Scheme 68. endo-dig Cycloisomerizations of 6-Silyloxy-1,5-enynes
Scheme 69
Scheme 69. Synthesis of Substituted Benzenes by Cycloisomerization of Propargyl Cyclopropenes
Scheme 70
Scheme 70. Synthesis of Alkynyl Cyclohexadienes by Rearrangement of Alkynylcyclopropanes
Scheme 71
Scheme 71. Conia-Ene Carbocyclizations of β-Keto Esters
Scheme 72
Scheme 72. Synthesis of Bicyclo[m.n.1]alkenone Frameworks by Conia-type Cyclization
Scheme 73
Scheme 73. Synthesis of Ventricosene
Scheme 74
Scheme 74. Syntheses of Hyperforin and Papuaforins A–C
Scheme 75
Scheme 75. Synthesis of Alkaloids (+)-Lycopladine and Fawcettimine
Scheme 76
Scheme 76. Syntheses of the Sesquiterpene (±)-Gomerone C and Alkaloid Daphenylline
Scheme 77
Scheme 77. Synthesis of (+)-Sieboldine A
Scheme 78
Scheme 78. [2 + 2] Cycloaddition of Alkynes with Alkenes
Scheme 79
Scheme 79. Formation of Lactones or Dienes by Reaction of Propiolic Acid with Alkenes
Scheme 80
Scheme 80. [2 + 2 + 2] Cycloaddition between Ynamides and Alkenes
Scheme 81
Scheme 81. Alkoxycyclization of 1,6-Enynes
Scheme 82
Scheme 82. Alkoxy or Hydroxycyclization of 1,6-Enynes by 6-endo-dig Pathway
Scheme 83
Scheme 83. Synthesis of Vinylsilanes from Allylsilylalkynes
Scheme 84
Scheme 84. Aminocyclization of 1,6-Enynes
Scheme 85
Scheme 85. [2 + 2 + 2] Cycloaddition of 1,6-Enynes with Carbonyl Compounds and Formation of Metathesis-Type Products
Scheme 86
Scheme 86. Reaction of 1,6-Enynes with Cyclopropenones
Scheme 87
Scheme 87. Reaction of 1,6-Enynes with Carbonyl Compounds via Rearrangement
Scheme 88
Scheme 88. Synthesis of 4-Oxa-6-azatricyclo[3.3.0.02,8]octanes from Alkynyl Hydroxyallyl Tosylamides
Scheme 89
Scheme 89. Intramolecular Amino- or Alkoxycyclization of 1,5-Enynes
Scheme 90
Scheme 90. Intramolecular Addition of Phenols to 1,5-Enynes
Scheme 91
Scheme 91. Synthesis of 5,6- and 6,6-Spiroketals from Hydroxypropargyl Vinyl Ethers
Scheme 92
Scheme 92. Cyclization of Oxo-1,6-enynes by [2 + 2 + 2] Alkyne/Alkene/Carbonyl Cycloaddition
Scheme 93
Scheme 93. Intermolecular [2 + 2 + 2] Cycloaddition of Terminal Alkynes with Oxoalkenes
Scheme 94
Scheme 94. Cyclization of 1,6-Enynes via 1,5-OR Migration
Scheme 95
Scheme 95. Syntheses of (+)-Orientalol F and Pubinernoid B
Scheme 96
Scheme 96. Synthesis of (−)-Englerin A
Scheme 97
Scheme 97. Synthesis of (+)-Schisanwilsonene A
Scheme 98
Scheme 98. Synthesis of Aromadendrane Sesquiterpenes
Scheme 99
Scheme 99. Intramolecular Cyclopropanation of 1,6-Enynes
Scheme 100
Scheme 100. Intermolecular Cyclopropanation of 1,6-Enynes
Scheme 101
Scheme 101. Intermolecular Cyclopropanation of 1,6-Enynes via Rearrangement
Scheme 102
Scheme 102. Intramolecular Cyclopropanation from 7-Alkynylcyclohepta-1,3,5-trienes
Scheme 103
Scheme 103. Intermolecular Addtion of Indole to 1,6-Enynes
Scheme 104
Scheme 104. Intramolecular [4 + 2] Cycloaddition of Arylalkynes with Alkenes
Scheme 105
Scheme 105. Synthesis of Dihydrobenzofluorenes by Cycloisomerization and Friedel-Crafts Alkylation
Scheme 106
Scheme 106. Addition of 1,3-Diketones to 1,6-Enynes by endo-Cyclization
Scheme 107
Scheme 107. Ligand-Controlled Addtion of 1,3-Diketones to 1,6-Enynes
Scheme 108
Scheme 108. Intramolecular [4 + 2] Cycloaddition of 1,3-Dien-8-ynes
Scheme 109
Scheme 109. General Pathways in the Isomerization of Propargylic Carboxylates
Scheme 110
Scheme 110. [3 + 2] Cycloaddition of Propargyl Acetals with Alkenes
Scheme 111
Scheme 111. Synthesis of Benzopyrans from Propargyl Carboxylates
Scheme 112
Scheme 112. Tandem Oxacyclization/[4 + 2]-Cycloaddition from in Situ Generated Ketoallene Substrates
Scheme 113
Scheme 113. Synthesis of ω-Hydroxy Propargylic Acetates via 1,3-Acetoxy Migration
Scheme 114
Scheme 114. Migration or Hydration of Halo-Substituted Propargyl Carboxylates
Scheme 115
Scheme 115. Synthesis of Divinyl Ketones from Alkynyloxiranes Bearing a Propargylic Carboxylate
Scheme 116
Scheme 116. Parallel Reaction Pathways of Enynes Bearing Propargylic Carboxylates
Scheme 117
Scheme 117. Synthesis of Bicyclo[3.1.0]hexan-2-ones by Cyclization of 1,5-Enynes with Propargylic Carboxylates
Scheme 118
Scheme 118. Synthesis of Cyclopentenones from 1,4-Enynes with Propargylic Carboxylates
Scheme 119
Scheme 119. Synthesis of Cyclopentenes from 1,3-Enynes with Propargylic Carboxylates
Scheme 120
Scheme 120. Synthesis of cis-Cyclohepta-4,8-diene-Fused Pyrrolidines from 1,3-Dien-8-yne Carbonates and Esters
Scheme 121
Scheme 121. Synthesis of Hydroazulenes by Cycloisomerization of 1,5-Enynes and Cope Rearrangement
Scheme 122
Scheme 122. Synthesis of Azabicyclo[4.2.0]oct-5-enes from N-Tethered 1,7-Enyne Benzoates
Scheme 123
Scheme 123. Synthesis of Hydroxy Dicarbonyl Compounds by Two 1,2-Acyloxy Migrations
Scheme 124
Scheme 124. Cyclization of 1,n-Enynes by 1,3-Acyloxy Migration and Michael Addition
Scheme 125
Scheme 125. Synthesis of Anthecotulide
Scheme 126
Scheme 126. Synthesis of Capnellene
Scheme 127
Scheme 127. Synthesis of 1,2-Dihydroquinolines from N-Propargyl Anilines
Scheme 128
Scheme 128. Synthesis of Pyrrolo[1,2-a]quinolones by Intramolecular Hydroarylation
Scheme 129
Scheme 129. Hydroarylation of Iodo-Substituted Propargyl Anilines
Scheme 130
Scheme 130. Synthesis of Coumarins or Spirolactones from Aryl Alkynoate Esters
Scheme 131
Scheme 131. Synthesis of Benzo-Fused Dihydrofurans from Alkynylhydrofurans
Scheme 132
Scheme 132. Synthesis of Phenanthrenes from o-Alkynyl Biphenyls
Scheme 133
Scheme 133. Synthesis of Diiodobenzo[k]tetraphenes
Scheme 134
Scheme 134. Synthesis of Phenanthrenes by 6-exo-dig Hydroarylation
Scheme 135
Scheme 135. Formation of Seven- and Eight-Membered Rings from Alkynyl Indoles by 7-exo-dig or 8-endo-dig Cyclization
Scheme 136
Scheme 136. Synthesis of Tetracyclic Indolines by Hydroarylation and Intramolecular Nucleophilic Addition
Scheme 137
Scheme 137. Synthesis of Substituted Spiroindolines from Ugi Four-Component Adducts
Scheme 138
Scheme 138. Synthesis of Dihydroindoloazepinones from Indole-3-carboxamides
Scheme 139
Scheme 139. Intermolecular Reaction of Homopropargyl Alcohols with Indoles
Scheme 140
Scheme 140. Intramolecular Phenol Synthesis from Alkynyl Furans
Scheme 141
Scheme 141. Intermolecular Phenol Synthesis from Alkynyl Furans
Scheme 142
Scheme 142. Divergent Reactions of Furan-ynes To Form Indenes or cis-Stilbene-Type Derivatives
Scheme 143
Scheme 143. Synthesis of Arylated (Z)-Enones from Furanyl Z-1,3-Enynes
Scheme 144
Scheme 144. Furan-yne Cyclization and Friedel-Crafts Annulation
Scheme 145
Scheme 145. Synthesis of Benzofurans by Friedel-Crafts Reaction of 4-Silyloxy-4-furyl Alkynes
Scheme 146
Scheme 146. Synthesis of Naphthols by Furan-yne Cyclization
Scheme 147
Scheme 147. Synthesis of Pyrrolopyridines by Intramolecular Hydroarylation of Pyrroles
Scheme 148
Scheme 148. Synthesis of Annulated Pyrroles via Hydroarylation
Scheme 149
Scheme 149. Intermolecular Hydroarylation of Pyrroles
Scheme 150
Scheme 150. Synthesis of Indoles by Cycloaddition between 1,3-Diynes and Pyrroles
Scheme 151
Scheme 151. Synthesis of the Tetracyclic Core of Berkelic Acid
Scheme 152
Scheme 152. Synthesis of Pimpinellin
Scheme 153
Scheme 153. Synthesis of Karapinchamine A
Scheme 154
Scheme 154. Generation of α-Oxo Gold(I) Carbenes and Gold(I) Carbenoids by Oxidation of Alkynes
Scheme 155
Scheme 155. Synthesis of Chroman-3-ones by Oxidative Cyclization
Scheme 156
Scheme 156. Synthesis of 2,5- and 2,4-Disubstituted Oxazoles by Oxidative Cyclization
Scheme 157
Scheme 157. Synthesis of Indoles from o-Alkynyl Anilines and Ynamides
Scheme 158
Scheme 158. Oxidative Cyclization of 3,5-Dien-1-ynes
Scheme 159
Scheme 159. Synthesis of Quinoline Frameworks by Oxidative Cycloaddition
Scheme 160
Scheme 160. Synthesis of Pyrroles by Acetylenic Schmidt Reaction
Scheme 161
Scheme 161. Synthesis of Indoloquinolines from o-(Azido)ynamides
Scheme 162
Scheme 162. Synthesis of (±)-Decinine
Scheme 163
Scheme 163. Synthesis of Sulfuretin
Scheme 164
Scheme 164. Total Syntheses of (−)-Citrinadine A and (+)-Citrinadine B
Scheme 165
Scheme 165. Synthesis of (−)-Nardoaristolone B by Oxidative Cyclization
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