NAD (P)+-NAD (P)H Models. 69. Mechanism of Stereospecific (NET) Hydride Transfer Controlled by Electronic Effect

Abstract
The enantiotopic C4-hydrogen in Me3MQPH is abstracted stereospecifically by certain oxidizing reagent such as metal ions and quinones. The stereospecificity depends on the reactivity of the oxidizing reagent. Namely, in the oxidation with Fe(III) or Co(III) ion, a Brønsted-like correlation is observed between the specificity and pKa of amine added to the reaction system, whereas the stereospecificity of the oxidation with quinones is not affected by amine. The mechanism of this electronically controlled stereospecificity is discussed.

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