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首页> 外文期刊>Organic Chemistry Frontiers >Mechanistic insights into the Rh(i)-catalyzed transannulation of 1,2,3-thiadiazoles with alkenes, alkynes, and nitriles: Does the intermediacy of alpha-thiavinyl Rh-carbenoids play an important role?
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Mechanistic insights into the Rh(i)-catalyzed transannulation of 1,2,3-thiadiazoles with alkenes, alkynes, and nitriles: Does the intermediacy of alpha-thiavinyl Rh-carbenoids play an important role?

机译：机械的见解Rh(我)催化transannulation的1、2、3-thiadiazoles烯烃、炔烃和腈类:独到的alpha-thiavinyl Rh-carbenoids扮演重要的角色吗?

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摘要

Density functional theory (DFT) calculations were performed to gain an in-depth mechanistic understanding of the Rh(i)-catalyzed transannulation of 1,2,3-thiadiazoles with alkenes, alkynes, and nitriles. Computational results indicate that the denitrogenation of 1,2,3-thiadiazoles promoted by the Rh(i) catalyst may not afford the commonly proposed alpha-thiavinyl Rh-carbenoid intermediate. Instead, the four-membered cyclometalated Rh(iii) complex is suggested to be the key intermediate, which could be formed via the cleavage of the S-N bond of 1,2,3-thiadiazoles to generate a six-membered cyclometalated Rh(iii) complex followed by N-2 extrusion. The easy chelation of the S atom with Rh is mainly responsible for the favorable formation of the four-membered cyclometalated Rh(iii) intermediate. Next, the substrates alkenes, alkynes, and nitriles could undergo migratory insertion with the four-membered rhodacycle followed by reductive elimination to furnish the corresponding products. The origins of divergent regioselectivities for the Rh(i)-catalyzed transannulation of 1,2,3-thiadiazoles with alkenes, alkynes, and nitriles are discussed, respectively, which are not only determined by the feasible migratory insertion pathway, but also by the feasibility of the subsequent reductive elimination.
机译：密度泛函理论(DFT)计算获得深入的机械执行对Rh (i)催化的理解transannulation的1、2、3-thiadiazoles烯烃、炔烃和腈。结果表明,脱氮1、2、3-thiadiazoles Rh (i)推广的催化剂一般不得承受提议吗alpha-thiavinyl Rh-carbenoid中间。相反,四元cyclometalated Rh (3)复杂的建议是关键的中间,这可能是通过形成s (n的乳沟吗的1、2、3-thiadiazoles生成六元cyclometalated Rh(3)复杂其次是n -挤压。S原子与Rh主要负责良好的四元环的形成cyclometalated Rh (iii)的中间体。基质烯烃、炔烃和腈进行迁移插入的四元rhodacycle还原紧随其后提供相应的消除产品。Rh (i)催化区域选择性transannulation的1、2、3-thiadiazoles烯烃、炔烃和腈进行了讨论,分别,不仅取决于可行的迁移插入路径,但是还有后续的可行性还原消除。

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