Phosphite mediated asymmetric N to C migration for the synthesis of chiral heterocycles from primary amines.

ABSTRACT: A phosphite mediated stereoretentive C-H alkylation of N-alkylpyridinium salts derived from chiral primary amines was achieved. The reaction proceeds through the activation of the N-alkylpyridinium salt substrate with a nucleophilic phosphite catalyst, followed by a base mediated [1,2] aza-Wittig rearrangement and subsequent catalyst dissociation for an overall N to C-2 alkyl migration. The scope and degree of stereoretention were studied, and both experimental and theoretical investigations were performed to support an unprecedented aza-Wittig rearrangement-rearomatization sequence. A catalytic enantioselective version starting with racemic starting material and chiral phosphite catalyst was also established following our understanding of the stereoretentive pr

SUBMITTER: Rani S 

PROVIDER: S-EPMC8261767 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature