Palladium-Catalyzed Oxidative Dehydrosilylation for Contra-Thermodynamic Olefin Isomerization,ACS Catalysis

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Palladium-Catalyzed Oxidative Dehydrosilylation for Contra-Thermodynamic Olefin Isomerization
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-07-21 , DOI: 10.1021/acscatal.0c02697
Steven Hanna _{1,

2} , Tyler Wills ₂ , Trevor W. Butcher ₂ , John F. Hartwig _{1,

2}

Affiliation

We report a newly developed, palladium-catalyzed dehydrosilylation of terminal alkylsilanes that combines with chain-walking hydrosilylation to create a one-pot isomerization of internal olefins to terminal olefins. This catalytic dehydrosilylation is one of the few examples of thermal catalytic functionalizations of unactivated alkylsilanes. The reaction involves transmetalation of an alkylsilane, β-hydride elimination, release of the terminal olefin, and reoxidation of the palladium catalyst. A variety of linear internal olefins underwent the overall isomerization to terminal olefins in good yields and in good regioselectivities. Particularly noteworthy, isomerizations occurring over seven carbon units proceeded in yields that are comparable to those of isomerizations occurring over one carbon unit.

中文翻译：

钯催化氧化脱氢硅烷化反应的热力学烯烃异构化

我们报道了一种新开发的，钯催化的末端烷基硅烷的脱氢硅烷化方法，其与链走氢化硅烷化方法相结合，可将内烯烃一锅异构化为末端烯烃。这种催化脱氢硅烷化是未活化的烷基硅烷的热催化官能化的少数实例之一。该反应包括烷基硅烷的金属转移，β-氢化物的消除，末端烯烃的释放以及钯催化剂的再氧化。各种线性内烯烃以良好的产率和良好的区域选择性经历了全部异构化为末端烯烃。特别值得注意的是，发生在七个碳单元上的异构化的收率与发生在一个碳单元上的异构化的收率相当。

更新日期：2020-08-08

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