Efficient <i>Z</i>-Selective Olefin-Acrylamide Cross-Metathesis Enabled by Sterically Demanding Cyclometalated Ruthenium Catalysts
作者:Yan Xu、Jonathan J. Wong、Adrian E. Samkian、Jeong Hoon Ko、Shuming Chen、K. N. Houk、Robert H. Grubbs
DOI:10.1021/jacs.0c11334
日期:2020.12.16
cyclometalated ruthenium catalysts with bulky N-heterocyclic carbene (NHC) ligands. Superior reactivity and stereoselectivity are realized for the first time in this challenging transformation, allowing streamlined access to an important class of cis-Michael acceptors from readily available feedstocks. The kinetic preference for cross-metathesis is enabled by a pivalate anionic ligand, and the origin
通过使用具有庞大 N-杂环卡宾 (NHC) 配体的新型环金属化钌催化剂,开发了丙烯酰胺和普通末端烯烃之间的高效 Z 选择性交叉复分解。在这一具有挑战性的转化中首次实现了卓越的反应性和立体选择性,允许从现成的原料中简化获得一类重要的顺式迈克尔受体。交叉复分解的动力学偏好是由新戊酸盐阴离子配体实现的,这种效应的起源通过密度泛函理论计算得到阐明。