- Regioselective Rh(I)-catalyzed sequential hydrosilylation toward the assembly of silicon-based peptidomimetic analogues
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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
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scheme or table
p. 5894 - 5906
(2012/09/21)
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- Homogeneous catalytic hydrosilylation of the C=C double bond in the presence of transition metal catalysts
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Hydrosilylation of unsaturated esters and other vinyl- and vinylidene type olefins has been carried out with PtCl2(PhCN)2, RhCl(PPh3)3 and platinum-phosphine catalysts.With PtCl2(PhCN)2 and platinum(0)-phosphine complexes as catalysts the hydrosilylation of methyl methacrylate gave the linear product 2a, whereas in the RhCl(PPh3)-catalyzed reaction the silyl ketene acetal derivative 4a was formed selectively.In the reactions of other esters and unsaturated hydrocarbons the main product is highly dependent on the structure of the substrate, but the catalyst used is also very important.With unsaturated hydrocarbons the selectivity is rather poor, but in the case of 1-vinyl-2-pyrrolidinone the linear- (9e) and the branched hydrosilylated derivative (10e) are formed in high yields depending on the catalyst used.The platinum(II)-phosphine complexes are inactive in the absence of air, but some platinum(0)-phosphine catalysts are also effective under argon in the hydrosilylation of methyl methacrylate.
- Skoda-Foeldes, Rita,Kollar, Laszlo,Heil, Balint
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p. 297 - 304
(2007/10/02)
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