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RESEARCH PRODUCT
Influence of Remote Substituents on the Equatorial/Axial Selectivity in the Monooxygenation of Methylene C−H Bonds of Substituted Cyclohexanes
Gregorio AsensioRossella MelloMinerva BáguenaJorge RoyoMaría Elena González-núñezCecilia AndreuGloria Castellanosubject
TrifluoromethylStereochemistrySubstituentGeneral ChemistryBiochemistryCatalysisTransition stateStereocenterchemistry.chemical_compoundColloid and Surface ChemistrychemistryDioxiraneCyclohexanesReactivity (chemistry)Methylenedescription
The reactivity of individual C--H bonds in the methyl(trifluoromethyl)dioxirane TFDO oxygenation of stereogenic methylene groups in conformationally homogeneous monosubstituted cyclohexanes (2) has been determined. The unexpectedly high occurrence of O-atom insertion into C--H(ax) bonds suggests an in plane trajectory attack in the oxygenation while the diastereoselectivity of the reaction is qualitatively interpreted on the basis of the distinct hyperconjugative stabilization by the substituent of diastereomeric transition states due to long-range through bond interactions.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2001-08-02 | Journal of the American Chemical Society |