Alkyl iodides and tertiary silanes were successfully coupled with good functional group tolerance using a Pt(P(tBu)(3))(2)/(iPr)(2)EtN/CH(3)CN system. The utility of the methodology is demonstrated by the synthesis of silafluofen, a Si-containing insecticide.

In the presence of an excess of pyridine ligand L, osmium tetroxide oxidizes tertiary silanes (Et(3)SiH, (i)Pr(3)SiH, Ph(3)SiH, or PhMe(2)SiH) to the corresponding silanols. With L = 4-tert-butylpyridine ((t)Bupy), OsO(4)((t)Bupy) oxidizes Et(3)SiH and PhMe(2)SiH to yield 100 +/- 2% of silanol and the structurally characterized osmium(VI) mu-oxo dimer [OsO(2)((t)Bupy)(2)](2)(mu-O)(2) (1a). With...

Reaction of 4-acyl-oxy-but-1-enyl-silanes with iodosylbenzene in the presence of BF(3) x OEt(2) gave 4-acyloxy-2-oxobutyl-silane and 3-acyloxy-tetrahydrofuran-2-yl-silane via a 1,3-di-oxan-2-yl cation intermediate, which is generated by participation of the acyloxy group during the electrophilic addition of iodine(III) to the substrate.

We report a highly enantioselective CuH-catalyzed Markovnikov hydrosilylation of vinylarenes and vinyl heterocycles. This method has a broad scope and enables both the synthesis of isolable silanes and the conversion of crude products to chiral alcohols. Density functional theory calculations support a mechanism proceeding by hydrocupration followed by σ-bond metathesis with a hydrosilane.

A Rh-catalyzed regiodivergent hydrosilylation of acyl aminocyclopropanes has been developed. Acyl aminocyclopropanes were reacted with hydrosilanes in the presence of Rh catalysts to afford ring-opened hydrosilylated adducts through carbon-carbon (C-C) bond cleavage of the cyclopropane ring. The regioselectivity of the addition of silanes (linear or branched) can be switched by changing the mon...