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DOI: 10.1055/s-0029-1219527
Gold-Catalyzed Reaction of Propargylic Carboxylates via an Initial 3,3-Rearrangement
Publication History
Publication Date:
18 February 2010 (online)
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Abstract:
Gold-catalyzed 3,3-rearrangement of propargylic carboxylates offers a versatile entry into a range of fascinating subsequent transformations, leading to various functional structures.
1 Introduction
1.1 Two Competing Mechanistic Pathways
1.2 Experimental Evidence for 3,3-Rearrangement
2 Synthetic Application via Gold-Containing Oxocarbenium Intermediates
2.1 General Considerations/Design
2.2 Using Indole-3-acetyl as the Acyl Group
2.3 Varying the R³ Group
2.3.1 Using Enyne Substrates (R³ = Alkenyl)
2.3.2 Using the TMSCH2 Group as R³
2.4 Using the Aryl Group for R¹ (R² = H)
2.5 Hydrolytic Treatment
2.5.1 Formation of Enones
2.5.2 Formation of α-Iodo/Bromoenones
2.6 Intramolecular Acyl Migration
2.7 Incorporating Gold(I)/Gold(III) Catalysis
2.7.1 Gold-Catalyzed Oxidative Homo-Coupling
2.7.2 Gold-Catalyzed Oxidative Cross-Coupling Reaction
2.7.3 Gold-Catalyzed Oxidative C-O Bond Formation
3 Attack of Au-Activated Carboxyallene at the β- or
γ-Position
3.1 Nucleophilic Attack at the γ-Position
3.2 Nucleophilic Attack at the β-Position
4 Carboxyallenes as Nucleophiles
5 Summary
Key words
rearrangements - carbocations - cyclizations - oxidations - allenes
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References
Current address: Department of Chemistry, Nanjing University, Nanjing, P. R. of China
2Previous address: Department of Chemistry, University of Nevada, Reno, NV 89557
20ConQuest® searching of the Cambridge structural database for structures containing C(sp²)-Au(I)(PPh3) bonds gave an average bond length of ˜2.04 Å, while the bond length of C(sp²)-C(sp³) is 1.50 Å.