Mechanism of Epoxidation of Norbornene with α-Hydroperoxy Diazenes

Article abstract of DOI:10.1021/jo00224a013

Thermolysis of α-hydroperoxy diazenes 1a-1c (Me2C(OOH)N=NR: 1a, R = CH2CF3; 1b, R = CH2CH2OCH3; 1c, R = CH2CH2OC6H5) at 50 deg C in benzene containing norbornene or in neat norbornene affords exo-(2R)-norbornane and exo-norbornene epoxide as major products and exo,exo-(2R)-3-hydroxynorbornane as a minor product.The reaction kinetics and the effects of deuteration of the hydroperoxy function on the distribution of products points to a radical chain process for the hydroalkylation and for the epoxidation.The other major product is formed by a competitive radical chain reaction.