Matviitsuk Anastassia, Lee Panger Jesse, Denmark Scott E
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, United States.
ACS Catal. 2022 Jun 17;12(12):7377-7385. doi: 10.1021/acscatal.2c01232. Epub 2022 Jun 7.
A method for the enantioselective, Lewis base-catalyzed sulfenofunctionalization of cyclic and ()-alkenes is reported. The intermediate thiiranium ion generated in the presence of a selenophosphoramide catalyst is intercepted by a variety of nucleophiles. A diverse array of inter- and intramolecular functionalizations proceed in high yield and good to high enantioselectivity (86:14-98:2 er). Prior experimental and computational studies indicated such enantiotopic face discrimination to be poor; however, the results disclosed herein remediate the previous findings. Control experiments were performed to investigate the different behavior of ()-alkenes and their more established ()-counterparts.
报道了一种用于环状烯烃和（）-烯烃的对映选择性、路易斯碱催化的亚磺酰官能化方法。在硒代磷酰胺催化剂存在下生成的中间体硫鎓离子被多种亲核试剂捕获。各种各样的分子间和分子内官能化反应以高产率和良好至高对映选择性（86:14 - 98:2 对映体过量）进行。先前的实验和计算研究表明这种对映异位面的区分较差；然而，本文公开的结果纠正了先前的发现。进行了对照实验以研究（）-烯烃及其更成熟的（）-对应物的不同行为。
