The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei, 430072, P. R. China.
College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan, 410083, P. R. China.
Angew Chem Int Ed Engl. 2022 Sep 12;61(37):e202209076. doi: 10.1002/anie.202209076. Epub 2022 Aug 3.
We report herein a modular catalytic method for the efficient enantioselective synthesis of chiral allylboronates from abundant feedstock chemicals through an asymmetric 1,1-difunctionalization of alkenes. This protocol is distinguished by its use of an inexpensive chiral catalyst, mild and convenient reaction conditions, wide substrate scope, scalability and practicality. The utility of this method is demonstrated by the rapid synthesis of key intermediates of complex drug molecules. Mechanistic studies reveal that β-H elimination is a highly regioselective step and the reversible homolysis and convergance to the lower energy pre-reductive elimination intermediate is the enantio-determining step.
我们在此报告了一种模块化催化方法，通过烯烃的不对称 1,1-双官能化反应，从丰富的原料化学品中高效、对映选择性地合成手性烯丙基硼酸酯。该方法的特点是使用廉价的手性催化剂、温和方便的反应条件、广泛的底物范围、可扩展性和实用性。该方法的实用性通过快速合成复杂药物分子的关键中间体得到了证明。机理研究表明，β-H 消除是一个高度区域选择性的步骤，可逆的均裂和收敛到较低能量的预还原消除中间体是对映选择性决定步骤。
