Stereoinvertive Nucleophilic Substitution at Quaternary Carbon Stereocenters of Cyclopropyl Ketones and Ethers

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2022 Apr 26

PMID 35471589

Authors

Xu Chen

Ilan Marek

Affiliations

Soon will be listed here.

Abstract

A highly regio- and diastereoselective nucleophilic substitution at the quaternary carbon stereocenter of cyclopropyl ketones and cyclopropyl carbinol derivatives using TMSBr, DMPSCl and TMSN as nucleophiles has been developed. A variety of acyclic tertiary alkyl bromides, chlorides and azides were therefore prepared with excellent diastereopurity. The substitution occurs at the most substituted quaternary carbon center in a stereoinvertive manner, which may be attributed to the existence of a bicyclobutonium species.

Citing Articles

Ligand-Metal Cooperation Enables Net Ring-Opening C-C Activation / Difunctionalization of Cyclopropyl Ketones.

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Highly Diastereoselective Preparation of Tertiary Alkyl Isonitriles by Stereoinvertive Nucleophilic Substitution at a Nonclassical Carbocation.

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