双金属串联催化实现的对映选择性环异构化/羰基-烯反应用于构建5-恶唑基甲基α-硅醇。

Sang Xinpeng, Mo Yuhao, Li Shiya, Liu Xiaohua, Cao Weidi, Feng Xiaoming

Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University Chengdu 610064 P. R. China

Chem Sci. 2023 Jul 7;14(31):8315-8320. doi: 10.1039/d3sc01048a. eCollection 2023 Aug 9.

A bimetallic tandem catalysis-enabled enantioselective cycloisomerization/carbonyl-ene reaction was developed. The reaction proceeded well with a broad range of -propargylamides and acylsilanes, affording the target chiral 5-oxazoylmethyl α-silyl alcohols in up to 95% yield and 99% ee under mild conditions. Importantly, this facile protocol was available for the late-stage modification of several bioactive molecules. Based on the mechanistic study and control experiments, a possible catalytic cycle and transition state are proposed to elucidate the reaction process and enantioinduction.

开发了一种双金属串联催化的对映选择性环异构化/羰基-烯反应。该反应对多种炔丙基酰胺和酰基硅烷都能顺利进行，在温和条件下以高达95%的产率和99%的对映体过量得到目标手性5-恶唑基甲基α-硅基醇。重要的是，这种简便的方法可用于几种生物活性分子的后期修饰。基于机理研究和对照实验，提出了一个可能的催化循环和过渡态，以阐明反应过程和对映体诱导。