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使用铱-铁催化的串联脱氢-异构化-硅氢化反应将烷烃转化为直链烷基硅烷。

Conversion of alkanes to linear alkylsilanes using an iridium-iron-catalysed tandem dehydrogenation-isomerization-hydrosilylation.

机构信息

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, 345 Lingling Road, Shanghai 200032, China.

出版信息

Nat Chem. 2016 Feb;8(2):157-61. doi: 10.1038/nchem.2417. Epub 2015 Dec 21.

Abstract

The conversion of inexpensive, saturated hydrocarbon feedstocks into value-added speciality chemicals using regiospecific, catalytic functionalization of alkanes is a major goal of organometallic chemistry. Linear alkylsilanes represent one such speciality chemical-they have a wide range of applications, including release coatings, silicone rubbers and moulding products. Direct, selective, functionalization of alkanes at primary C-H bonds is difficult and, to date, methods for catalytically converting alkanes into linear alkylsilanes are unknown. Here, we report a well-defined, dual-catalyst system for one-pot, two-step alkane silylations. The system comprises a pincer-ligated Ir catalyst for alkane dehydrogenation and an Fe catalyst that effects a subsequent tandem olefin isomerization-hydrosilylation. This method exhibits exclusive regioselectivity for the production of terminally functionalized alkylsilanes. This dual-catalyst strategy has also been applied to regioselective alkane borylations to form linear alkylboronate esters.

摘要

将廉价的饱和烃原料转化为具有附加值的特种化学品,方法是通过烷烃的区域特异性、催化官能化来实现,这是金属有机化学的主要目标。线性烷基硅烷就是这样一种特种化学品,它们有广泛的应用,包括脱模涂层、硅橡胶和模塑制品。在伯 C-H 键上直接、选择性地官能化烷烃是困难的,迄今为止,催化转化烷烃为线性烷基硅烷的方法还不为人知。在这里,我们报告了一种用于一锅两步烷烃硅烷化的定义明确的双催化剂体系。该体系由一个钳状配体化的 Ir 催化剂用于烷烃脱氢,以及一个 Fe 催化剂用于随后的串联烯烃异构化-硅氢化。这种方法表现出对末端官能化烷基硅烷的独特区域选择性。这种双催化剂策略也已应用于区域选择性的烷烃硼化反应,以形成线性烷基硼酸酯。

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