Roselli Christina A, Gagné Michel R
Department of Chemistry. University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290, USA.
Org Biomol Chem. 2016 Nov 29;14(47):11261-11265. doi: 10.1039/c6ob02128j.
A diastereoselective, gold-catalyzed cascading cycloisomerization of alkylidene cyclopropane bearing 1,5-enynes that terminates in a cyclo-addition of aldehydes has been developed. This diastereoselective reaction provides convergent access to novel polycyclic molecular structures (18 examples), and tolerates a diverse scope of aldehydes. Mechanistic studies reveal that the catalytic cycle rests at a digold off-cycle intermediate, one of which was isolated.
已开发出一种非对映选择性的、金催化的含1,5-烯炔的亚烷基环丙烷的级联环异构化反应,该反应以醛的环加成反应结束。这种非对映选择性反应为新型多环分子结构(18个实例)提供了汇聚式合成途径,并且能耐受多种醛。机理研究表明,催化循环停留在一种双金非循环中间体上,其中一种中间体已被分离出来。