US EPA

8405181 

Journal Article 

Homogeneous Redox Catalysis Study of the Reductive Cyclization of 6-Hepten-2-one. Unusual Effects of the Nature and Concentration of the Catalyst 

Swartz, JE; Kariv-Miller, E; Harrold, SJ 

1989 

Yes 

Journal of the American Chemical Society
ISSN: 0002-7863
EISSN: 1520-5126 

111 

4 

1211-1216 

English 

10.1021/ja00186a007 

https://www.scopus.com/inward/record.uri?eid=2-s2.0-0000242881&doi=10.1021%2fja00186a007&partnerID=40&md5=b9e4562f933ca946b23d7de1fe74d3bb
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Electrochemical reductive cyclization of 6-hepten-2-one can be effected by homogeneous redox catalysts. Effective catalysts include biphenyl, 2-methoxybiphenyl, naphthalene, and phenanthrene. The reaction consumed 2 F mol−1, and cis-and trans-dimethylcyclopentanol were formed as exclusive products. The percentage of the cyclic alcohol that was cis increased with increasing redox catalyst concentration, increasingly positive reduction potentials of the catalyst, and increasing amounts of water present in the medium. These results are explained by invoking a mechanism involving reversible cyclization of the ketyl radical anion formed from reduction of 6-hepten-2-one. The cis or trans cyclized radical anions can be trapped by further reduction or by protonation to (ultimately) form the observed products. © 1989, American Chemical Society. All rights reserved.