Carbene‐Catalyzed Activation of C−Si Bonds for Chemo‐ and Enantioselective Cross Brook–Benzoin Reaction

作者：Chenghao Tang, Wei Wang, Guoyong Luo, Chaoyang Song, Zhaowei Bao, Pei Li, Ge‐Fei Hao, Yonggui Robin, Zhichao Jin · 发表于：Angewandte Chemie International Edition · 年份：2022 · DOI：10.1002/anie.202206961 · 被引用次数：24 · 研究领域：N-Heterocyclic Carbenes in Organic and Inorganic Chemistry、Synthetic Organic Chemistry Methods、Catalytic Cross-Coupling Reactions

The first carbene-catalyzed asymmetric chemoselective cross silyl benzoin (Brook-Benzoin) reaction has been developed. Key steps of this reaction involve activation of the carbon-silicon bond of an acylsilane by a chiral N-heterocyclic carbene (NHC) catalyst to form a silyl acyl anion intermediate. These acyl anions then undergo an addition reaction with indole aldehydes in a highly chemo- and enantioselective manner to afford α-silyloxy ketones with excellent optical purities. The reaction mechanism of this cross Brook-Benzoin reaction was investigated through both experimental and computational methods. The chiral α-hydroxy ketone derivatives obtained by this approach show promising, agrochemically interesting activity against harmful plant bacteria.