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

Xiangqing Jia & Zheng Huang

Nature Chemistry Volume: 8, Pages: 157–161  Year published: (2016) doi:10.1038/nchem.2417 Received 04 August 2015    Accepted  11 November 2015  Published online 21 December 2015      

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.

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