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Photoinduced Remote Functionalization of Amides and Amines Using Electrophilic Nitrogen Radicals.

ABSTRACT: The selective functionalization of C(sp³ )-H bonds at distal positions to functional groups is a challenging task in synthetic chemistry. Reported here is a photoinduced radical cascade strategy for the divergent functionalization of amides and protected amines. The process is based on the oxidative generation of electrophilic amidyl radicals and their subsequent transposition by 1,5-H-atom transfer, resulting in remote fluorination, chlorination and, for the first time, thioetherification, cyanation, and alkynylation. The process is tolerant of most common functional groups and delivers useful building blocks that can be further elaborated. The utility of this strategy is demonstrated through the late-stage functionalization of amino acids and a dipeptide.

SUBMITTER: Morcillo SP

PROVIDER: S-EPMC6221136 | biostudies-literature | 2018 Sep

REPOSITORIES: biostudies-literature

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Photoinduced Remote Functionalization of Amides and Amines Using Electrophilic Nitrogen Radicals.

Morcillo Sara P SP Dauncey Elizabeth M EM Kim Ji Hye JH Douglas James J JJ Sheikh Nadeem S NS Leonori Daniele D

Angewandte Chemie (International ed. in English) 20180829 39

The selective functionalization of C(sp<sup>3</sup> )-H bonds at distal positions to functional groups is a challenging task in synthetic chemistry. Reported here is a photoinduced radical cascade strategy for the divergent functionalization of amides and protected amines. The process is based on the oxidative generation of electrophilic amidyl radicals and their subsequent transposition by 1,5-H-atom transfer, resulting in remote fluorination, chlorination and, for the first time, thioetherific ...[more]

PMID: 30074300

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