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一种通过铑催化的烷氧基硅烷分子间C-H硅基化反应来制备各种功能性芳基烷氧基硅烷的直接方法。

A direct method to access various functional arylalkoxysilanes by Rh-catalysed intermolecular C-H silylation of alkoxysilanes.

作者信息

Som Salina, Choi Jongwook, Katsoulis Dimitris, Lee Kangsang L

机构信息

University of Central Florida, Department of Chemistry 4111 Libra Drive, PSB #255 Orlando FL USA 32816

Dow Chemical Company 2200 West Salzburg Road Auburn MI USA 48611.

出版信息

Chem Sci. 2022 Aug 23;13(36):10759-10764. doi: 10.1039/d2sc03727k. eCollection 2022 Sep 21.

DOI:10.1039/d2sc03727k
PMID:36320708
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9491085/
Abstract

Efficient protocols for intermolecular C-H silylations of unactivated arenes and heteroarenes with HMeSiOEt are disclosed. The silylations are catalysed by a Rh-complex (0.5 mol%) derived from commercially available [Rh(coe)Cl] and (,)-Ph-BPE in the presence of cyclohexene at 100 °C, furnishing desired arylethoxydimethylsilanes up to 99% yield. The regioselectivity is mainly affected by the steric bulk of the substituents in arenes and by electronic effects as an ancillary factor. Mechanistic study revealed that the mono-hydrido dimeric Rh-complex, [Rh(Ph-BPE)(μ-H)(μ-Cl)], is an active catalytic intermediate, which further suppresses the formation of redistribution byproducts in the silylation. Preliminary results show that the current protocol can be extended to double C-H silylations affording bis-silylated arenes and is applicable to the silylation of HMeSi(OEt) to deliver the corresponding (aryl)SiMe(OEt).

摘要

公开了使用HMeSiOEt对未活化芳烃和杂芳烃进行分子间C-H硅氢化反应的有效方案。该硅氢化反应由市售的[Rh(coe)Cl]和(,)-Ph-BPE衍生的Rh络合物（0.5 mol%）在环己烯存在下于100°C催化，得到所需的芳基乙氧基二甲基硅烷，产率高达99%。区域选择性主要受芳烃中取代基的空间位阻影响，电子效应作为辅助因素。机理研究表明，单氢二聚体Rh络合物[Rh(Ph-BPE)(μ-H)(μ-Cl)]是活性催化中间体，它进一步抑制了硅氢化反应中再分配副产物的形成。初步结果表明，当前方案可扩展至双C-H硅氢化反应以提供双硅烷化芳烃，并且适用于HMeSi(OEt)的硅氢化反应以得到相应的(芳基)SiMe(OEt)。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3fb5/9491085/d10e61e8480d/d2sc03727k-s6.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3fb5/9491085/877f996c2ab9/d2sc03727k-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3fb5/9491085/d10e61e8480d/d2sc03727k-s6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3fb5/9491085/4476f09cab5d/d2sc03727k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3fb5/9491085/ca6656edd87f/d2sc03727k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3fb5/9491085/f7a296fc307d/d2sc03727k-s3.jpg
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