Silylating Disulfides and Thiols with Hydrosilicones Catalyzed by B(C6F5)3

Abstract Hydrosilanes and silicones, catalyzed with B(C 6 F 5 ) 3 , may be used to silylate thiols or cleave disulfides giving silyl thio ethers. Alcohols were found to react faster than thiols or disulfides, while alkoxysilanes (the Piers‐Rubinsztajn reaction) were slower such that the overall order of reactivity was found to be HO>HS>SS>SiOEt. The resulting silane and silicone‐protected thio ethers produced from the sulfur‐based functional groups could be cleaved to thiols using alcohols or mild acid with rates that depend on the steric bulk of the siloxane.