State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China.
J Am Chem Soc. 2021 Jan 20;143(2):1195-1202. doi: 10.1021/jacs.0c12333. Epub 2020 Dec 30.
An enantioselective addition reaction of various alkyl groups to unactivated internal alkenes under Cu catalysis has been developed. The reaction uses amide-linked aminoquinoline as the directing group, 4-alkyl Hantzsch esters as the donor of alkyl radicals, and rarely used biaryl diphosphine oxide as a chiral ligand. β-lactams featuring two contiguous stereocenters at Cβ and the β substituent can be obtained in good yield with excellent enantioselectivity. Mechanistic studies indicate that a nucleophilic addition of the alkyl radical to Cu-coordinated alkene is the enantio-determining step.
已开发出在铜催化下各种烷基与非活化的内部烯烃的对映选择性加成反应。该反应使用酰胺连接的氨基喹啉作为导向基团，4-烷基 Hantzsch 酯作为烷基自由基的供体，以及很少使用的联芳基双膦氧化物作为手性配体。具有 Cβ和β取代基处两个相邻手性中心的β-内酰胺可以以良好的收率和优异的对映选择性获得。机理研究表明，烷基自由基对铜配位烯烃的亲核加成是对映体决定步骤。
