一种立体选择性的[3+1]环扩张反应用于高度取代的亚甲基氮杂环丁烷的合成。
A Stereoselective [3+1] Ring Expansion for the Synthesis of Highly Substituted Methylene Azetidines.
机构信息
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI, 53706, USA.
出版信息
Angew Chem Int Ed Engl. 2017 Sep 25;56(40):12229-12233. doi: 10.1002/anie.201705202. Epub 2017 Sep 1.
Abstract
The reaction of rhodium-bound carbenes with strained bicyclic methylene aziridines results in a formal [3+1] ring expansion to yield highly substituted methylene azetidines with excellent regio- and stereoselectivity. The reaction appears to proceed through an ylide-type mechanism, where the unique strain and structure of the methylene aziridine promotes a ring-opening/ring-closing cascade that efficiently transfers chirality from substrate to product. The resultant products can be elaborated into new azetidine scaffolds containing vicinal tertiary-quaternary and even quaternary-quaternary stereocenters.
摘要
铑卡宾与张力环双环亚甲基氮丙啶反应，通过叶立德型机理，以优异的区域和立体选择性得到高取代的亚甲基氮杂环丁烷，发生形式[3+1]环扩张。其中，亚甲基氮丙啶独特的张力和结构促进开环/闭环级联反应，有效地将手性从底物转移到产物中。得到的产物可以进一步转化为含有相邻三级-季碳和甚至四级-季碳立体中心的新型氮杂环丁烷骨架。
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