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Highly Enantioselective Synthesis of 1,2,3‐Substituted Cyclopropanes by Using α‐Iodo‐ and α‐Chloromethylzinc Carbenoids
Author(s) -
Beaulieu LouisPhilippe B.,
Zimmer Lucie E.,
Gag Alexandre,
Charette André B.
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201202528
Subject(s) - electrophile , enantioselective synthesis , negishi coupling , formal synthesis , stereoselectivity , chemistry , lithium (medication) , stereochemistry , combinatorial chemistry , ligand (biochemistry) , organic chemistry , catalysis , biology , biochemistry , receptor , endocrinology
Abstract Herein, we report the enantio‐ and diastereoselective formation of trans ‐iodo‐ and trans ‐chlorocyclopropanes from α‐iodo‐ and α‐chlorozinc carbenoids by using a dioxaborolane‐derived chiral ligand. The synthetically useful iodocyclopropane building blocks were derivatized by an electrophilic trapping of the corresponding cyclopropyl lithium species or a Negishi coupling to give access to a variety of enantioenriched 1,2,3‐substituted cyclopropanes. The synthetic utility of this method was demonstrated by the formal synthesis of an HIV‐1 protease inhibitor. In addition, the related stereoselective bromocyclopropanation was also investigated. New insights about the relative electrophilicity of haloiodomethylzinc carbenoids are also presented.