6533b824fe1ef96bd128143c
RESEARCH PRODUCT
Hyperconjugative Control by Remote Substituents of Diastereoselectivity in the Oxygenation of Hydrocarbons.
Jorge RoyoCecilia AndreuCarmen BoixMaría Elena González-núñezGloria CastellanoRossella MelloGregorio Asensiosubject
chemistry.chemical_compoundchemistryStereochemistryOrganic ChemistrySubstituentDiastereomerStereoselectivityPhysical and Theoretical ChemistryBiochemistryTransition statedescription
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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2000-05-18 | Organic letters |