An unusual example of stereoelectronic control in the ring opening of 3,3-disubstituted 1,2-dichlorocyclopropenes

Abstract
Quantitative SCF-MO calculations at the PM3 and ab initio level reveal that the origin of the stereoselective ring opening of 1,2-dichloro-3,3-disubstituted cyclopropenes (1, R2= CH2Cl, CH2OMe or CH2Ph) to give vinylcarbenes 2via transition state 5 arises from stereoelectronic control, in contrast to that of cyclopropenes having bulky non-polar substituents such as R2= Pri which favours a less hindered transition state 6.

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