Cu-Mediated Rearrangements of Allenylcyclopropanols to Cyclopentenones: Two Divergent Pathways

Naresh Tumma; Eppa Gyanchander; Jin Kun Cha

doi:10.1021/acs.joc.7b00432

Cu-Mediated Rearrangements of Allenylcyclopropanols to Cyclopentenones: Two Divergent Pathways

J Org Chem. 2017 Apr 21;82(8):4379-4385. doi: 10.1021/acs.joc.7b00432. Epub 2017 Mar 30.

Authors

Naresh Tumma¹, Eppa Gyanchander¹, Jin Kun Cha¹

Affiliation

¹ Department of Chemistry, Wayne State University , 5101 Cass Ave, Detroit, Michigan 48202, United States.

PMID: 28335601
DOI: 10.1021/acs.joc.7b00432

Abstract

Two CuCN-mediated rearrangement reactions of allenylcyclopropanols to cyclopentenones have been achieved by means of Et₂Zn/CuCN·2LiCl or CuCN·2LiCl to afford 5-alkyl or 4-alkyl cyclopentenone regioisomers: the former conditions afford 5-alkyl substituted cyclopentenones via β-carbon elimination, whereas the latter result in the 4-alkyl substituted regioisomers with concomitant oxidation at the γ-position, via a free radical mechanism.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, Non-U.S. Gov't