Cu-Mediated Rearrangements of Allenylcyclopropanols to Cyclopentenones: Two Divergent Pathways
Naresh Tumma1, Eppa Gyanchander1, Jin Kun Cha1
1Department of Chemistry, Wayne State University , 5101 Cass Ave, Detroit, Michigan 48202, United States.
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.
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