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芳烃和杂芳烃与单（三甲基硅氧基）硅烷、双（三甲基硅氧基）硅烷和三（三甲基硅氧基）硅烷的分子间C-H硅氢化反应：在多种操作方法下控制硅烷的重新分布

Intermolecular C-H silylations of arenes and heteroarenes with mono-, bis-, and tris(trimethylsiloxy)hydrosilanes: control of silane redistribution under operationally diverse approaches.

作者信息

Swann Noah, Tang Kiki, Nam Jihyeon, Lee Jooyeon, Domin Marek, Shaw Thomas E, Kozimor Stosh A, Som Salina, Lee Kangsang L

机构信息

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

Mass Spectrometry Centre, Boston College 245 Beacon Street, Chestnut Hill MA 02467 USA.

出版信息

Chem Sci. 2024 Jul 1;15(30):11912-11918. doi: 10.1039/d4sc03394a. eCollection 2024 Jul 31.

DOI:10.1039/d4sc03394a
PMID:39092102
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11290416/
Abstract

Efficient catalytic protocols for C-H silylations of arenes and heteroarenes with sterically and electronically different hydrosiloxysilanes are disclosed. The silylations are catalyzed by a well-defined Rh-complex (1 mol%), derived from [Rh(1,5-hexadiene)Cl] and a bulky BINAP type ligand. This catalyst not only promotes C-Si bond formation affording the desired products in up to 95% isolated yield, but also can suppress the silane redistribution side reactions of HSiMe(OTMS). The protocol can also be applied for the C-H silylations of more reactive HSiMe(OTMS) with a much lower catalyst loading (0.25 mol%) and even with sterically demanding HSi(OTMS). The steric bulk of the arene substituent and hydrosiloxysilane is a major factor in determining the regioselectivity and electronic effect as secondary. The current method can be performed under operationally diverse conditions: with/without a hydrogen scavenger or solvent.

摘要

公开了用于芳烃和杂芳烃与空间和电子性质不同的氢硅氧基硅烷进行C-H硅氢化反应的高效催化方案。硅氢化反应由一种明确的Rh络合物（1 mol%）催化，该络合物由[Rh(1,5-己二烯)Cl]和一种大位阻的联萘酚型配体衍生而来。这种催化剂不仅能促进C-Si键的形成，以高达95%的分离产率得到所需产物，还能抑制HSiMe(OTMS)的硅烷再分布副反应。该方案还可用于更具反应性的HSiMe(OTMS)的C-H硅氢化反应，催化剂负载量更低（0.25 mol%），甚至适用于空间位阻较大的HSi(OTMS)。芳烃取代基和氢硅氧基硅烷的空间位阻是决定区域选择性的主要因素，电子效应是次要因素。目前的方法可以在多种操作条件下进行：有/无氢清除剂或溶剂。

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