01692nas a2200205   4500008004100000022001400041245011200055210006900167260000800236300001400244490000700258520097800265100001701243700002501260700001601285700002201301700001701323700001801340856012801358       2021                        eng d  a2041-652000aPhosphite mediated asymmetric N to C migration for the synthesis of chiral heterocycles from primary amines0 aPhosphite mediated asymmetric N to C migration for the synthesis  cJUL  a8996-90030 v123 aA 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 process. This method provides efficient access to tertiary and quaternary stereogenic centers in pyridine systems, which are prevalent in drugs, bioactive natural products, chiral ligands, and catalysts.1 aRani, Soniya1 aDash, Soumya, Ranjan1 aBera, Asish1 aAlam, Md, Nirshad1 aVanka, Kumar1 aMaity, Pradip  uhttps://library.ncl.res.in/content/phosphite-mediated-asymmetric-n-c-migration-synthesis-chiral-heterocycles-primary-amines