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Direct Deamination of Primary Amines via Isodiazene Intermediates.

ABSTRACT: We report here a reaction that selectively deaminates primary amines and anilines under mild conditions and with remarkable functional group tolerance including a range of pharmaceutical compounds, amino acids, amino sugars, and natural products. An anomeric amide reagent is uniquely capable of facilitating the reaction through the intermediacy of an unprecedented monosubstituted isodiazene intermediate. In addition to dramatically simplifying deamination compared to existing protocols, our approach enables strategic applications of iminium and amine-directed chemistries as traceless methods. Mechanistic and computational studies support the intermedicacy of a primary isodiazene which exhibits an unexpected divergence from previously studied secondary isodiazenes, leading to cage-escaping, free radical species that engage in a chain, hydrogen-atom transfer process involving aliphatic and diazenyl radical intermediates.

SUBMITTER: Berger KJ

PROVIDER: S-EPMC8892627 | biostudies-literature | 2021 Oct

REPOSITORIES: biostudies-literature

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Direct Deamination of Primary Amines via Isodiazene Intermediates.

Berger Kathleen J KJ Driscoll Julia L JL Yuan Mingbin M Dherange Balu D BD Gutierrez Osvaldo O Levin Mark D MD

Journal of the American Chemical Society 20211012 42

We report here a reaction that selectively deaminates primary amines and anilines under mild conditions and with remarkable functional group tolerance including a range of pharmaceutical compounds, amino acids, amino sugars, and natural products. An anomeric amide reagent is uniquely capable of facilitating the reaction through the intermediacy of an unprecedented monosubstituted isodiazene intermediate. In addition to dramatically simplifying deamination compared to existing protocols, our appr ...[more]

PMID: 34637305

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