Hyperconjugative Control by Remote Substituents of Diastereoselectivity in the Oxygenation of Hydrocarbons
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Updated: Aug 7, 2026

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
Published on: November 21, 2017
González-Nuñez1, Royo, Castellano
1Departamento de Química Orgánica, Universidad de Valencia, Avda. V. Andrés Estellés s/n, 46100-Burjassot (Valencia), Spain.
Abstract:
The oxidation of 2-substituted adamantanes (2) with TFDO (1) is reported. The data show a stereodifferentiation of the chemical environments induced by remote electron-withdrawing substituents which produces remarkable Z/E diastereoselectivity in the oxidation of the tertiary C(5)-H and C(7)-H bonds. The results show a bell-shaped correlation between the Z/E stereoselectivity and the substituent constant sigma(I), which is interpreted in terms of hyperconjugative stabilization of the diastereomeric transition states.
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