Copper(I) Catalyzed Differential Peroxidation of Terminal and Internal Alkenes Using TBHP. Issue 2 (7th January 2020)

• Record Type: Journal Article
• Authors: Mir, Bilal Ahmad; Rajamanickam, Suresh; Begum, Pakiza; Patel, Bhisma K.
• Is Part Of: European journal of organic chemistry. Issue 2(2020)
• Page Start: 252
• Page End: 261
• Publication Date: 2020-01-07
• Subjects: Carbonylation -- Peroxidation -- Cycloalkylation -- Cycloetherification -- Copper; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201901689
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : 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. Abstract : 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.