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A Versatile Enantioselective Catalytic Cyclopropanation‐Rearrangement Approach to the Divergent Construction of Chiral Spiroaminals and Fused Bicyclic Acetals

Li Zhou, Wen‐Guang Yan, Xiu‐Li Sun, Lijia Wang, Yong Tang

2020Angewandte Chemie International Edition31 citationsDOI

Abstract

A highly enantioselective synthesis of various chiral heterobicyclic molecules including spiroaminals and fused bicyclic acetals has been developed via a chiral copper catalyzed cyclopropanation-rearrangement (CP-RA) approach under mild reaction conditions. Remarkably, the asymmetric CP-RA for exocyclic vinyl substrates without a pro-stereogenic carbon at the β-position has been realized for the first time and a broad substrate scope with excellent results (33 examples; 34-99 % yields; >95/5 dr and 91-99 % ee) has been achieved. An application of a successive enantioselective CP-RA approach was also described, providing a concise access to complex chiral heteropolycycles.

Topics & Concepts

CyclopropanationEnantioselective synthesisBicyclic moleculeCatalysisChemistryCombinatorial chemistryOrganic chemistryStereochemistryCyclopropane Reaction MechanismsAsymmetric Synthesis and CatalysisSynthetic Organic Chemistry Methods