Liu Qian, Teng Kunpeng, Zhang Yi, Lv Ya, Chi Yonggui Robin, Jin Zhichao
State Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Center for R&D of Fine Chemicals of Guizhou University, Guiyang, 550025, China.
School of Chemistry, Chemical Engineering, and Biotechnology, Nanyang Technological University, Singapore, 637371, Singapore.
Angew Chem Int Ed Engl. 2024 Nov 11;63(46):e202406386. doi: 10.1002/anie.202406386. Epub 2024 Sep 17.
An unprecedented chemodivergent strategy for parallel kinetic resolution (PKR) is disclosed through which two planar chiral products bearing different structures were simultaneously afforded with opposite stereoselectivities. Two achiral esters are activated by one single chiral N-heterocyclic carbene (NHC) catalyst to react with the different enantiomers of the racemic imine substrate in a parallel fashion. Two products bearing distinct structures and opposite stereoselectivities are respectively afforded from the same reaction system in good to excellent yields, enantio- and diastereoselectivities. Control experiments and kinetic studies are carried out to probe the kinetic and dynamic properties during the reaction progress. The planar chiral pyridine and lactam products show interesting applications in both asymmetric synthesis and pesticide development.
本文报道了一种前所未有的用于平行动力学拆分（PKR）的化学发散策略，通过该策略可同时得到两种具有相反立体选择性的不同结构的平面手性产物。一种单一的手性N-杂环卡宾（NHC）催化剂可活化两种非手性酯，使其与外消旋亚胺底物的不同对映体以平行方式反应。从同一反应体系中可分别以良好至优异的产率、对映选择性和非对映选择性得到两种具有不同结构和相反立体选择性的产物。进行了对照实验和动力学研究，以探究反应过程中的动力学和动态性质。平面手性吡啶和内酰胺产物在不对称合成和农药开发中均显示出有趣的应用。
