The hydrosilylation of alkenes is an important reaction in the production of organosilicon compounds. However, directly using silanes, such as SiH₄, MeSiH₃, etc., is problematic because they are flammable or even pyrophoric gases at room temperature.

Xile Hu and colleagues, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland, have developed a nickel-catalyzed hydrosilylation reaction that replaces the silanes with alkoxy hydrosilanes, such as Me(EtO)₂SiH and (MeO)₃SiH. The team used a nickel pincer complex (pictured) as a catalyst and sodium tert-butoxide (NaO^tBu) as a base. These conditions allowed the hydrosilylation of a range of terminal alkenes at room temperature with yields up to 93 %.

The researchers propose a mechanism which involves a base-catalyzed disproportionation reaction of the alkoxysilanes to give hydrosilanes, followed by the nickel-catalyzed hydrosilylation of the alkenes. The hydrosilane intermediates were detected using ¹H NMR spectroscopy. The reaction could serve as a safer alternative to directly using silanes, has a broad scope and good functional group tolerance.

• Alkoxy Hydrosilanes As Surrogates of Gaseous Silanes for Hydrosilylation of Alkenes,
  Ivan Buslov, Sébastien Carlos Keller, Xile Hu,
  Org. Lett. 2016.
  DOI: 10.1021/acs.orglett.6b00792