Deformylation Reaction by a Nonheme Manganese(III)–Peroxo Complex via Initial Hydrogen-Atom Abstraction
Journal: Angewandte Chemie
Publication Date: 08 July, 2016
Department of: Chemical Engineering and Analytical Science
A new mechanism for an important enzyme reaction
In biomimetic and enzymatic reactivity, aldehyde deformylation is a common reaction process. Until recently it was thought that the mechanism, which involves side-on interaction with a manganese-peroxo intermediate, proceeds through a nucleophilic attack on the aldehyde carbonyl group. Now, researchers at the University of Manchester have combined experimental and computational studies to come with an alternative mechanism starting with a rate-determining hydrogen atom abstraction reaction. The researchers use valence bond models to explain the mechanism and show that it is governed by the relative electron affinity of the substrate carbonyl group with respect to the manganese ion. Now they plan further research to find out how general their new mechanism is.