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. 2022 May 25;12(12):6816–6830. doi: 10.1021/acscatal.2c00257

Scheme 2. Enzyme Strategies to Facilitate Hydride Transfer Oxidation by Deprotonation of the Alcohol Substrate.

Scheme 2

(a) General base catalysis, concerted reaction; (b) electrostatic stabilization by the metal ion, stepwise reaction; (c) two-step catalytic mechanism of substrate oxidation by TaCPa2E, with an initial enzyme–substrate complex (E..S) undergoing coupled motions to populate the reactive enzyme–substrate conformer (ES) that converts chemically to the keto-intermediate complex E*I. A strong (low barrier-like) hydrogen bond may be characteristic of the ES complex, distinct from the “normal” hydrogen bond present in E*I.