仿生拆分羧酸
Biomimetic Desymmetrization of a Carboxylic Acid.
机构信息
Department of Chemistry & Vanderbilt Institute of Chemical Biology, Vanderbilt University , Nashville, Tennessee 37235-1822, United States.
Indiana University Molecular Structure Center , Bloomington, Indiana 47405, United States.
出版信息
J Am Chem Soc. 2018 Feb 14;140(6):1998-2001. doi: 10.1021/jacs.7b12185. Epub 2018 Feb 5.
Abstract
The enantioselective desymmetrization of carboxylic acids by chiral Brønsted base catalysis is reported, leading to bridged bicyclic lactones with up to 94% ee. Crystallographic analysis of a substrate-catalyst complex suggests an origin of stereocontrol, reminiscent of functional Brønsted bases in biological settings, and enabled reaction optimization. The products contain an all-carbon quaternary stereocenter and can be derivatized to functionalized cyclopentanes.
摘要
手性 Brønsted 碱催化的羧酸对映选择性去对称化反应，得到桥环双环内酯，ee 值高达 94%。底物-催化剂配合物的晶体学分析表明了立体控制的起源，类似于生物环境中的功能 Brønsted 碱，并实现了反应优化。产物含有全碳季碳立体中心，可衍生为功能化的环戊烷。
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