Copper(I)-Catalyzed Asymmetric Desymmetrization: Synthesis of Five-Membered-Ring Compounds Containing All-Carbon Quaternary Stereocenters

A highly stereoselective catalytic alkylation sequence for the synthesis of highly functionalized and versatile five-membered-ring compounds bearing all-carbon quaternary stereocenters was developed. Enantioselective desymmetrization of achiral cyclopentene-1,3-diones was thus executed by chiral Cu–phosphoramidite catalysts. A variety of complicated cyclopentane derivatives can be synthesized with excellent stereoselectivities using a low catalyst loading in a one-pot operation.本研究开发了一种高立体选择性催化烷基化序列，用于合成带有全碳季碳立体中心的高官能团化、用途广泛的五元环化合物。据此，研究人员采用手性铜-亚磷酰胺催化剂，实现了非手性环戊烯-1,3-二酮的对映选择性去对称化反应。通过一锅法操作并使用低催化剂负载量，即可合成一系列具有优异立体选择性的复杂环戊烷衍生物。