4.8 Article

Highly Selective Synthesis of Hydrosiloxanes by Au-Catalyzed Dehydrogenative Cross-Coupling Reaction of Silanols with Hydrosilanes

Journal

ACS CATALYSIS
Volume 7, Issue 3, Pages 1836-1840

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.6b03560

Keywords

Hydrosiloxanes; Hydrosilanes; Silanols; Au-Catalyst; Cross-Coupling

Funding

  1. Development of Innovative Catalytic Processes for Organosilicon Functional Materials project from the New Energy and Industrial Technology Development Organization (NEDO)

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We report a highly selective synthesis of siloxane building blocks containing SiH2 or SiH functionalities. AuCl-(PPh3)/PPh3 or AuCl(PPh3)/(PBu3)-Bu-n system catalyzed the reaction of trihydrosilanes with silanols giving SiHrcontaining siloxanes exclusively. On the other hand, a highly selective reaction of dihydrosilanes with silanols to afford SiH-containing siloxanes was achieved by simply changing the phosphine ligand to a bidentate one, xantphos. Usefulness of SiH2-containing siloxanes was demonstrated by the synthesis of a trisiloxane, Et3SiOSi(Ph)(H)(OSiBuMe2)-Bu-t, and a pentasiloxane, Ph2Si-(OSiHPhOSiEt3)(2,) bearing SiH functionalities.

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