Radical [1,3] Rearrangements of Breslow Intermediates
by Alwarsh, Sefat; Xu, Yi; Qian, Steven Y.; McIntosh, Matthias C.
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.
- Journal
- Angewandte Chemie-International Edition
- Volume
- 55
- Issue
- 1
- Year
- 2016
- Start Page
- 355-358
- URL
- https://dx.doi.org/10.1002/anie.201508368
- ISBN/ISSN
- 1521-3773; 1433-7851
- DOI
- 10.1002/anie.201508368