title: 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.
authors.affiliation: Department of Chemistry and Biochemistry, University of Arkansas, 345 N Campus Dr., Fayetteville, AR 72701 (USA).
authors.forename: Sefat
authors.initials: S
authors.lastname: Alwarsh
authors.affiliation: Department of Pharmaceutical Sciences, NDSU Dept 2665, 208B Sudro Hall, North Dakota State University, P.O. Box 6050, Fargo, ND 58108-6050 (USA).
authors.forename: Yi
authors.initials: Y
authors.lastname: Xu
authors.affiliation: Department of Pharmaceutical Sciences, NDSU Dept 2665, 208B Sudro Hall, North Dakota State University, P.O. Box 6050, Fargo, ND 58108-6050 (USA).
authors.forename: Steven Y
authors.initials: SY
authors.lastname: Qian
authors.affiliation: Department of Chemistry and Biochemistry, University of Arkansas, 345 N Campus Dr., Fayetteville, AR 72701 (USA). mcintosh@uark.edu.
authors.forename: Matthias C
authors.initials: MC
authors.lastname: McIntosh
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D002262:Carboxy-Lyases / Q000737:chemistry / Q000378:metabolism; D005609:Free Radicals / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D011789:Quantum Theory; D013831:Thiamine / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000438:Alcohols; D005609:Free Radicals; D002262:Carboxy-Lyases; C019778:benzoylformate decarboxylase; D013831:Thiamine
keywords: Breslow intermediates; N-heterocyclic carbenes; radicals; rearrangement; thiamine