Fang Tongchang, Zhang Peng, Liu Chao
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, China.
TUniversity of Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2025 Jan 15;64(3):e202415301. doi: 10.1002/anie.202415301. Epub 2024 Nov 4.
The stereoselective cyclopropanation of olefins with "boron ylide" is disclosed for the first time, providing a modular strategy for the synthesis of stereospecific diboryl-functionalized cyclopropanes. The chiral gem-diborylcyclopropanes are synthesized with excellent enantioselectivity with the aid of a chiral auxiliary. Based on the powerful transformable ability of boryl group, those challenging multi-quaternary carbon centers in cyclopropane units have been facilely constructed with excellent stereoselectivity. Control experiments indicate that the boryl groups are necessary for both chemoselectivity and stereoselectivity control.
首次公开了烯烃与“硼叶立德”的立体选择性环丙烷化反应，为合成立体特异性二硼官能化环丙烷提供了一种模块化策略。在手性助剂的帮助下，以优异的对映选择性合成了手性偕二硼环丙烷。基于硼基强大的可转化能力，环丙烷单元中那些具有挑战性的多季碳中心已能轻松构建，并具有优异的立体选择性。对照实验表明，硼基对于化学选择性和立体选择性控制都是必需的。
