56040-98-3Relevant articles and documents
Application d'une methode de calcul au choix d'un modele cinetique en photochimie II. Intervention de radicaux pyramidaux dans la photoreduction des cyclohexanones
Micheau, J. C.,Paillous, N.,Lattes, A.
, p. 257 - 263 (2007/10/02)
The photreduction of cyclohexanones leads usually to the corresponding diastereomeric cyclohexanols.In ethers, photoadducts are also isolated.The stereoselectivity of photoreduction depends on experimental conditions (concetration of the various reactants, addition of radical scavengers).The variation of stereoselectivity can be interpreted at the radical step by assuming that the radical center is either planar or pyramidal.These two assumptions were compared by using the previously described method of numerical analysis.Thus the involvement of a pyramidal radical center carrying stereochemical information, can be postulated with a high degree of reliability.This hypothesis which implies that pyramidal radicals posses some configurational stability was confirmed by a selective deuteriation experiment.A pyramidalisation angle between 17 deg and 42 deg according to the invertomer in consideration, was measured by independent ESR measurements.The results definitively confirm the non-planar character of the hydroxycycloheyl radical showing the reliability of the "ACADEMIC" method.
