71771-69-2Relevant articles and documents
Regioselective Rh(I)-catalyzed sequential hydrosilylation toward the assembly of silicon-based peptidomimetic analogues
Min, Geanna K.,Skrydstrup, Troels
experimental part, p. 5894 - 5906 (2012/09/21)
A highly regioselective Rh(I)-catalyzed hydrosilylation of enamides is presented. This mild protocol allows access to a wide variety of different arylsilanes with substitution at the β-position of the enamide and functionalization on the alkyl chain tethered to the silane. This protocol is extended to include a sequential one-pot hydrosilylation. Using diphenylsilane as the appendage point, hydrosilylation of a protected allyl alcohol followed by hydrosilylation of an enamide generates a complex organosilane in one step. This highly convergent strategy to synthesize these functionalized systems now provides a way for the rapid assembly of a diverse collection of silane-based peptidomimetic analogues.
Reactions of heteroarylhydrosilanes with dichlorocarbene under phase-transfer conditions
Lukevics, E.,Sturkovich, R.,Goldberg, Yu.,Gaukhman, A.
, p. 19 - 26 (2007/10/02)
The reactions of dimethyl(2-thienyl)-, methyl-, tri(2-thienyl)- and dimethyl(2-furyl)silanes (I-IV, respectively) with dichlorocarbene generated from sodium trichloroacetate under solid-liquid phase-transfer conditions afford the corresponding dichloromethylsilanes in 38-66percent yield.The reactivity of the thienylsilanes decreases with the number of electron-accepting thienyl substituents at the silicon atom.Using the competition reactions, the relative rate constants for the reaction of dichlorocarbene insertion into the Si-H bond of thienyl- and furyl-silanes (I and IV) were measured.The reactivity of these silanes was found to be greater than had been expected taking as a basis the Taft ?* constants for the substituent at the silicon atom.This is apparently due to the existence of a p?-d? interaction between the heterocyclic ?-system and the d-orbitals of silicon.
