A Catalytic Synthesis of Thiosilanes and Silthianes:  Palladium Nanoparticle-Mediated Cross-Coupling of Silanes with Thio Phenyl and Thio Vinyl Ethers through Selective Carbon−Sulfur Bond Activation

Palladium nanoparticles generated in situ from N,N-dimethyl-acetamide (DMA) solutions of PdX(2) (X = Cl(-), OAc(-), OCOCF(3)(-)) or Pd(2)(dba)(3) by reduction with alkyl silanes R(3)SiH (R = Me, Et, i-Pr, t-Bu) are selective catalysts for the cross-coupling of the silanes R(3)SiH with phenyl and vinyl thioethers forming the corresponding thiosilanes and silthianes in high yields and under mild conditions. The method is applicable to phenyl thioglycosides, giving access to thiosilyl glycosides a new class of sugar derivatives.