铜介导的烯丙基环丙醇重排为环戊烯酮：两种不同途径。
Cu-Mediated Rearrangements of Allenylcyclopropanols to Cyclopentenones: Two Divergent Pathways.
机构信息
Department of Chemistry, Wayne State University , 5101 Cass Ave, Detroit, Michigan 48202, United States.
出版信息
J Org Chem. 2017 Apr 21;82(8):4379-4385. doi: 10.1021/acs.joc.7b00432. Epub 2017 Mar 30.
PMID:28335601
Abstract
Two CuCN-mediated rearrangement reactions of allenylcyclopropanols to cyclopentenones have been achieved by means of EtZn/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.
摘要
通过 EtZn/CuCN·2LiCl 或 CuCN·2LiCl 实现了烯丙基环丙醇的两种 CuCN 介导的重排反应，得到了环戊烯酮：前者条件通过β-碳消除生成 5-烷基取代的环戊烯酮，而后者则通过自由基机制生成γ-位同时氧化的 4-烷基取代的区域异构体。
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