Radical [1,3] Rearrangements of Breslow Intermediates.

ABSTRACT: Breslow intermediates that bear radical-stabilizing N substituents, such as benzyl, cinnamyl, and diarylmethyl, undergo facile homolytic C-N bond scission under mild conditions to give products of formal [1,3] rearrangement rather than benzoin condensation. EPR experiments and computational analysis support a radical-based mechanism. Implications for thiamine-based enzymes are discussed.

SUBMITTER: Alwarsh S 

PROVIDER: S-EPMC4715472 | biostudies-literature | 2016 Jan

REPOSITORIES: biostudies-literature