Experimental and Computational Studies on Rh(I)-Catalyzed Reaction of Siloxyvinylcyclopropanes and Diazoesters,Journal of the American Chemical Society

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Experimental and Computational Studies on Rh(I)-Catalyzed Reaction of Siloxyvinylcyclopropanes and Diazoesters
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-12-04 , DOI: 10.1021/jacs.0c08089
Sheng Feng ₁ , Kang Wang ₁ , Yifan Ping ₁ , Jianbo Wang ₁

Affiliation

The Rh(I)-catalyzed reaction of siloxyvinylcyclopropanes and diazoesters leads to the formation of siloxyvinylcyclobutane and 1,4-diene derivatives. With [Rh(cod)Cl]2 as the catalyst, the formation of 1,4-diene was favored over the formation of siloxyvinylcyclobutane. By changing the catalyst to [Rh(cod)2OTf], siloxyvinylcyclobutane derivatives are formed with excellent chemoselectivities and in moderate to good yields. The alkene products are also obtained as single E configured isomers. A detailed mechanism for this transformation is proposed on the basis of mechanistic experiments and DFT calculations. The effect of catalysts on the chemoselectivity of these reactions is also examined computationally.

中文翻译：

Rh(I)-催化甲硅烷氧基乙烯基环丙烷和重氮酯反应的实验和计算研究

甲硅烷氧基乙烯基环丙烷和重氮酯的 Rh(I) 催化反应导致形成甲硅烷氧基乙烯基环丁烷和 1,4-二烯衍生物。以[Rh(cod)Cl]2 作为催化剂，1,4-二烯的形成优于甲硅烷氧基乙烯基环丁烷的形成。通过将催化剂改为 [Rh(cod)2OTf]，可以形成具有优异化学选择性和中等至良好产率的甲硅烷氧基乙烯基环丁烷衍生物。烯烃产物也以单一的 E 构型异构体形式获得。在机械实验和 DFT 计算的基础上提出了这种转换的详细机制。还通过计算检查了催化剂对这些反应的化学选择性的影响。

更新日期：2020-12-04

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