Copper(I) Catalyzed Differential Peroxidation of Terminal and Internal Alkenes Using TBHP

Terminal and internal alkenes react contrarily with tert‐butyl hydroperoxide (TBHP) giving various products. A Cu(I) catalyzed decarbonylative C–C bond formation followed by a carbonylation–peroxidation of vinyl arenes has been achieved using tert‐butyl hydroperoxide (TBHP) as the oxidant in acetonitrile. Whereas, α‐methyl styrenes yielded aryl methyl ketones and the α‐substituted unsymmetrical internal alkenes afforded selective α‐peroxidation under the identical reaction conditions. Concurrent peroxidation–carbonylation–cycloalkylation/cycloetherifiction of internal cyclic alkene such as indene is achieved by switching the solvent system from acetonitrile to cycloalkanes/cyclic ether. All these reactions proceed via radical paths generating interesting peroxo‐compounds. A TBHP mediated carbonylation–peroxidation of styrene, α‐peroxidation of α‐substituted unsymmetrical internal alkenes and concurrent peroxidation–carbonylation–cycloalkylation/cycloetherifiction of internal cyclic alkene (indene) have been developed.