Sefat Alwarsh1, Yi Xu2, Steven Y Qian2, Matthias C McIntosh3. 1. Department of Chemistry and Biochemistry, University of Arkansas, 345 N Campus Dr., Fayetteville, AR 72701 (USA). 2. Department of Pharmaceutical Sciences, NDSU Dept 2665, 208B Sudro Hall, North Dakota State University, P.O. Box 6050, Fargo, ND 58108-6050 (USA). 3. Department of Chemistry and Biochemistry, University of Arkansas, 345 N Campus Dr., Fayetteville, AR 72701 (USA). mcintosh@uark.edu.
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.
Breslow intermediates that bear radical-stabilizing N substituents, such as benzyl, n class="Chemical">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.
Authors: Danilo Meyer; Piotr Neumann; Eline Koers; Hanno Sjuts; Stefan Lüdtke; George M Sheldrick; Ralf Ficner; Kai Tittmann Journal: Proc Natl Acad Sci U S A Date: 2012-06-22 Impact factor: 11.205