Hyperconjugative Control by Remote Substituents of Diastereoselectivity in the Oxygenation of Hydrocarbons

• DOI: 10.1021/ol000017m
• Publication Date: 2002-07-26T06:08:25Z
• Authors: María E. González...; Jorge Royo; Gloria Castellano; Cecilia Andreu; Carmen Boix; Rossella Mello; Gregorio Asensio
• Keywords: 01 natural sciences; 0104 chemical sciences

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.