The Wolff-Rearrangement Reaction of Oxidatively Generated α-Oxo Gold Carbenes: An Effective Approach to Silylketenes

• Published in: Angewandte Chemie International Edition Vol. 58; no. 16; pp. 5241 - 5245
• Main Authors: Zheng, Yang, Zhang, Junqi, Cheng, Xinpeng, Xu, Xinfang, Zhang, Liming
• Format: Journal Article
• Language: English
• Published: 18.03.2019
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201814018

Gold-catalyzed oxidations of alkynes by N -oxides offer a direct access to reactive α-oxo gold carbene intermediates from benign and readily available alkynes instead of hazardous diazo carbonyl compounds. Despite various versatile synthetic methods developed based on this strategy, one of the hallmarks of α-oxo carbene/carbenoid chemistry, i.e., the Wolff rearrangement, has not been realized in this context. This study discloses the first examples that the Wolff rearrangement can be readily realized by α-oxo gold carbenes oxidatively generated from TBS-terminated alkynes. The thus-generated silylketenes can be isolated pure or subsequently trapped by various internal or external nucleophiles in one pot to afford α-silylated carboxylic acids, their derivatives or TBS-substituted allenes. The Wolff rearrangement is observed for the first time upon gold-catalyzed oxidation of terminally TBS-substituted alkyne. The silyl group is essential for this reaction, and the generated silylketenes are stable and can be isolated or subsequently trapped in a variety of manners to afford γ-lactones, α -silylated carboxylic acids and their derivatives, or silylallenes.