膦催化的乙烯基环丙烷的活化：乙烯基环丙基酮重排为环庚烯酮
Phosphine-Catalyzed Activation of Vinylcyclopropanes: Rearrangement of Vinylcyclopropylketones to Cycloheptenones.
作者信息
Wu Jun, Tang Yuhai, Wei Wen, Wu Yong, Li Yang, Zhang Junjie, Zheng Yuansuo, Xu Silong
机构信息
Department of Chemistry, School of Science, Xi'an Key Laboratory of Sustainable Energy Materials Chemistry, Xi'an Jiaotong University, Xi'an, 710049, P. R. China.
出版信息
Angew Chem Int Ed Engl. 2018 May 22;57(21):6284-6288. doi: 10.1002/anie.201800555. Epub 2018 May 2.
We report a phosphine-catalyzed activation of electron-deficient vinylcyclopropanes (VCPs) to generate an ambident C synthon that is poised to undergo consecutive reactions. The utility of the activation is demonstrated in a phosphine-catalyzed rearrangement of vinylcyclopropylketones to cycloheptenones in good yields with a broad substrate scope. Mechanistic investigations support a stepwise process comprising homoconjugate addition, water-assisted proton transfer, and 7-endo-trig S 2' ring closure.
我们报道了一种膦催化的缺电子乙烯基环丙烷（VCPs）的活化反应，生成一种双亲性碳合成子，该合成子可进行连续反应。这种活化反应的实用性在膦催化的乙烯基环丙基酮重排为环庚烯酮的反应中得到了证明，该反应产率良好，底物范围广泛。机理研究支持了一个逐步过程，包括同共轭加成、水辅助质子转移和7-endo-trig S2'环化反应。
Zotero 插件