Zn(II)- or Rh(I)-Catalyzed Rearrangement of Silylated [1,1鈥?Bi(cyclopropan)]-2鈥?en-1-ols

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• 作者：Hang Zhang ; Changkun Li ; Guojun Xie ; Bo Wang ; Yan Zhang ; Jianbo Wang
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：July 3, 2014
• 年：2014
• 卷：79
• 期：13
• 页码：6286-6293
• 全文大小：406K
• ISSN：1520-6904

文摘

The rearrangement reactions of silylated alcohols bearing the highly strained structures of cyclopropene and cyclopropanol connected in adjacent positions have been studied under ZnI₂- and Rh(I)-catalyzed conditions. The results show intriguing carbon skeletal reorganizations of such system under these conditions. The ZnI₂-catalyzed reaction proceeds with C鈥揙 cleavage and the rearrangement of the resultant carbon cation, leading to the breaking of the C鈥揅 single bond that connects two three-memebered rings. In contrast, the Rh(I)-catalyzed reaction involves 蟽-bond oxidative addition of the cyclopropene moiety, followed by 尾-carbon elimination of the cyclopropane moiety.