Carbene-catalyzed activation of C-Si bonds for chemo- and enantioselective cross Brook–Benzoin reaction

• Main Authors: Tang, Chenghao, Wang, Wei, Luo, Guoyong, Song, Chaoyang, Bao, Zhaowei, Li, Pei, Hao, Gefei, Chi, Robin Yonggui, Jin, Zhichao
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2022
• Subjects: Science::Chemistry; Acylsilanes; Benzoin Condensation
• Online Access: https://hdl.handle.net/10356/163498
• Institution: Nanyang Technological University

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.