Mechanistic Aspects Regarding the Elimination of H2O2 from C(4a)-Hydroperoxyflavin. The Role of a Proton Shuttle Required for H2O2 Elimination

• Published in: Journal of organic chemistry Vol. 78; no. 17; pp. 8585 - 8593
• Main Authors: Bach, Robert D, Mattevi, Andrea
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 06.09.2013
• Subjects: Flavins - chemistry; Hydrogen Peroxide - chemistry; Molecular Structure; Protons; Quantum Theory

DFT calculations presented for C(4a)-hydroperoxyflavin (C(4a)-FLHOOH) at the B3LYP/6-311+G(d,p) level suggest a new mechanism for the elimination of H2O2. The calculated activation barrier for a concerted four-centered elimination (ΔE ‡ = 32.86 kcal/mol) strongly suggests that in the absence of inte...