Huang Xiaolei, Oh William Ray Jun Jie, Zhou Jianrong Steve
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, SPMS-CBC-06-03, Singapore, 637371, Singapore.
Angew Chem Int Ed Engl. 2018 Jun 25;57(26):7673-7677. doi: 10.1002/anie.201804318. Epub 2018 May 28.
Enantioselective α-arylation of racemic ketones containing existing α'-stereocenters is reported for the first time via base-induced dynamic kinetic resolution. Bridged bicyclic rings are formed in good ee values, which are difficult to obtain otherwise. Furthermore, reactions in DMSO-d resulted in extensive deuteration of both α- and α'-positions in the products, thus supporting a pathway involving rapid, reversible deprotonation of ketones under catalytic conditions.
首次报道了通过碱诱导的动态动力学拆分实现含有现有α'-立体中心的外消旋酮的对映选择性α-芳基化反应。以良好的对映体过量值（ee值）形成了桥连双环，否则很难得到。此外，在氘代二甲亚砜（DMSO-d）中的反应导致产物的α位和α'-位均发生广泛的氘代，从而支持了在催化条件下酮快速、可逆去质子化的反应途径。
