Premium
Radical [1,3] Rearrangements of Breslow Intermediates
Author(s) -
Alwarsh Sefat,
Xu Yi,
Qian Steven Y.,
McIntosh Matthias C.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201508368
Subject(s) - homolysis , chemistry , bond cleavage , electron paramagnetic resonance , benzoin , medicinal chemistry , photochemistry , radical , organic chemistry , catalysis , nuclear magnetic resonance , physics
Breslow intermediates that bear radical‐stabilizing N substituents, such as benzyl, cinnamyl, and diarylmethyl, undergo facile homolytic CN 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.