Theoretical study of the insertion reaction of CH3O–H by singlet alkylidenecarbenes

The mechanisms for the insertion reactions of alkylidenecarbenes with CH3O–H have been investigated at the B3LYP/6-311G(d,p) level of the theory. According to our model calculations these insertion reactions will easily yield vinyl ether products and for a given single substituted alkylidenecarbene will yield cis–trans-isomer mixture. Moreover the reactivity of alkylidenecarbene decreases in the order: HFCC > HClCC > HBrCC > H(CH3)CC > H2CC. Furthermore, a configuration mixing model based on the work of Pross and Shaik is used to rationalize the computational results.