Gold(I)-Catalyzed Addition of Silylacetylenes to Acylsilanes: Synthesis of Indanones by CH Functionalization through a Gold(I) Carbenoid

• Published in: Angewandte Chemie International Edition Vol. 54; no. 46; pp. 13678 - 13681
• Main Authors: González, Jairo, Santamaría, Javier, Ballesteros, Alfredo
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 09-11-2015; WILEY‐VCH Verlag
• Subjects: acylsilanes; Alkynes; carbenoids; Formations; gold; homogeneous catalysis; Migration; Reaction mechanisms; Synthesis; gold; carbenoids; acylsilanes; homogeneous catalysis; alkynes
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201505830

A gold(I)‐catalyzed synthesis of indanones from trimethylsilylacetylenes and acylsilanes is presented. The reaction is initiated through a synergistic acylsilane activation–gold acetylide formation and involves consecutive alkyne σ‐gold(I) addition, π‐activation, and 1,2‐migration of a silyl group. Studies performed on the reaction mechanism allowed to establish the nature of the silyl migrating group and invoke the participation of a gold(I) carbenoid intermediate. The reaction is completed by a gold(I) CH functionalization step.
The elegant way: A gold(I)‐catalyzed synthesis of indanones from trimethylsilylacetylenes and acylsilanes was developed. The reaction involves a synergistic acylsilane activation–gold acetylide formation and consecutive alkyne σ‐gold(I) addition, π‐activation, and 1,2‐silyl migration. Mechanistic studies suggest the participation of a gold(I) carbenoid intermediate.