Premium
1,3‐Difunctionalization of Aminocyclopropanes via Dielectrophilic Intermediates
Author(s) -
Wang MingMing,
Waser Jérôme
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201907060
Subject(s) - chemistry , enantioselective synthesis , acetal , nucleophile , halide , alkoxy group , phosphoric acid , ring (chemistry) , combinatorial chemistry , carbamate , catalysis , sulfonyl , organic chemistry , medicinal chemistry , stereochemistry , alkyl
Abstract We report an oxidative ring‐opening strategy to transform acyl, sulfonyl or carbamate protected aminocyclopropanes into 1,3‐dielectrophilic carbon intermediates bearing a halide atom (Br, I) and a N,O‐acetal. Replacing the alkoxy group of the N,O‐acetal can be achieved under acidic conditions through an elimination–addition pathway, while substitution of the halides by nucleophiles can be done under basic conditions through a S N 2 pathway, generating a wide range of 1,3‐difunctionalized propylamines. A proof of concept for asymmetric induction was realized using a chiral phosphoric acid (CPA) as catalyst, highlighting the potential of the method in enantioselective synthesis of important building blocks.