Bidirectional Electron Transfer Strategies for Anti-Markovnikov Olefin Aminofunctionalization via Arylamine Radicals.

ABSTRACT: Arylamines are common structural motifs in pharmaceuticals, natural products, and materials precursors. While olefin aminofunctionalization chemistry can provide entry to arylamines, classical polar reactions typically afford Markovnikov products. Nitrogen-centered radical intermediates provide the opportunity to access anti-Markovnikov selectivity; however, anti-Markovnikov arylamination is unknown in large part due to the lack of arylamine radical precursors. Here, we introduce bidirectional electron transfer processes to generate arylamine radical intermediates from N-pyridinium arylamines: Single-electron oxidation provides arylamine radicals that engage in anti-Markovnikov olefin aminopyridylation; single-electron reduction unveils arylamine radicals that engage in anti-Markovn

SUBMITTER: Roychowdhury P 

PROVIDER: S-EPMC11385361 | biostudies-literature | 2024 Sep

REPOSITORIES: biostudies-literature