Thermolysis and Photolysis of 3-Chloro-3-benzyldiazirines in Alkenes: Evidence for a Carbene-Alkene Complex

Article abstract of DOI:10.1021/jo00228a013

Photolysis and thermolysis of substituted 3-chloro-3-benzyldiazirines in alkenes yielded cyclopropanes and chlorostyrenes as products.The results suggest that the cyclopropanation of benzylchlorocarbenes is independent of substituents.However, 1,2-hydrogen migration is accelerated by OCH3 or CH3 substituents, and is decelerated by a Cl substituent on the phenyl ring.These results support the existence of an energy barrier to 1,2-H migration.Evidence is provided for carbene-alkene complexation.