Regioselective Rh(I)-catalyzed sequential hydrosilylation toward the assembly of silicon-based peptidomimetic analogues
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.
Min, Geanna K.,Skrydstrup, Troels
experimental part
p. 5894 - 5906
(2012/09/21)
An NMR study of the formation of silyloxonium ions by using tetrakis[3,5-bis(trifluoromethyl)phenyl]borate as counteranion
The capability of tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (TFPB) as a counteranion for organosilicenium ions was investigated by NMR spectroscopy. Although reactions of hydrosilanes with trityl-TFPB did not give the corresponding silicenium ions as
Kira, Mitsuo,Hino, Takakazu,Sakurai, Hideki
p. 6697 - 6700
(2007/10/02)
Reactions of heteroarylhydrosilanes with dichlorocarbene under phase-transfer conditions
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.
Lukevics, E.,Sturkovich, R.,Goldberg, Yu.,Gaukhman, A.
p. 19 - 26
(2007/10/02)
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