Department of Applied Chemistry, Tokyo Institute of Technology, Tokyo, 152-8552, Japan.
Chem Asian J. 2018 Oct 4;13(19):2842-2846. doi: 10.1002/asia.201801035. Epub 2018 Sep 19.
The highly enantioselective Diels-Alder reaction of acetylenic dienophiles is shown to be effectively catalyzed by cationic chiral palladium complexes. Not only the degree but also the sense of enantioselectivity critically depends on the steric demand of ligands. Computational analyses indicate that the steric demand does not affect the endo/exo-selectivity but the enantioface selectivity of dienes.
手性钯配合物能有效地催化炔属二烯亲双烯体的高对映选择性 Diels-Alder 反应。不仅对映选择性的程度,而且对映选择性的方向都强烈依赖于配体的空间位阻要求。计算分析表明,空间位阻要求并不影响双烯的内/外选择性,而影响其对映面选择性。