Theoretical Studies of Autoxidation of 2-Alkylidene-13-cyclohexadioneLeading to Bicyclic-Hemiketal Endoperoxides

摘要

Mechanism of the addition of molecular oxygen on the dienolic form of the 2-alkylidene-1,3-cyclohexadione was investigated by quantum chemical calculations using the approximate projection method developed by Yamaguchi. The complete reaction pathway of the formation of the endoperoxide is described. The crossing between triplet and singlet potential energy surfaces has been located. A multireference complete active space self-consistent field calculation has been performed to strengthen the results.