Silylation hydro

Double. silylation of the a-diketone 120 with (Me3Si)2 is catalyzed by PdCl2(Me3P)2 to give the l,2-bis(siloxy)ethylene 121 in a good yield[ll7], Hydro.silylation of phenyl isocyanate (122) catalyzed by PdCN affords the /V-... 

Silicon—Carbon Bond-Forming Reactions. After the Rochow-MbUer direct process, the hydro silylation reaction (139),... 

Palladium oxazoline compounds (e.g., (47)) have been used to catalyze the cyclization/hydro-silylation of functionalized 1,6-dienes (Scheme 31). With R = Pr1, >95% diastereomeric excess and 87% ee was achieved at low temperature. Changing the ligand bulk with R = Bu1 gave a higher ee value, but poorer diastereoselectivity. A range of functional groups can be tolerated at both the allylic and terminal alkene positions.135-137... 

The stereochemistry is assumed to involve retention of configuration. This assumption is very plausible, since retention has already been observed for Pt insertion in a Si-H bond, as well as for homogeneous and heterogeneous hydro-silylation and hydrogermylation . Moreover, the Si-H bond is known to react generally with retention of configuration . Finally, in a parent reaction of SiH with C02(C0)g, X-ray structural analysis reveals that the reaction proceeds with retention of configuration (see Sect. 2.2.2). 

Although, among the catalyhc conversions of (organo)silicon compounds, hydro-silylation remains the most commercially used process, a variety of other reactions catalyzed by transihon-metal complexes have been idenhfied and developed during the past two decades. 

In chapter 2, M. Tanaka summarizes the current state of the art of the homogeneous catalysis of H-P bond addition reactions, thus showing that as hydro-silylation and hydroboration, the H-P addition reactions are among the indispensable modern synthetic reactions needed by researchers in organic and main group element chemistry. 

We have already seen various syntheses of SMA phthalimides, either through nucleophilic animation of a-chlorosilanes (see Sections III.A.l and III.A.2), hydro-silylation of A-vinyl phthalimide (see Section III.B.5.f) or by reaction of SMA with phthalic anhydride (see Section IV.A.2.h). The deprotection and recovery of free SMA has been conducted in the usual way by reaction with hydrazine.81,88,211... 

The cationic ruthenium complex [CpRu(MeCN)3]+(PF6) catalyses the hydro-silylation of alkyne with triethylsilane in good yield and with very limited formation of Unear 1,2-disubstituted products (Eq. 17, Table 4). 

We have obtained silsesquioxane-based polymer (HS-Polymer) by using the hydro-silylation reaction of vinyl-functionalized macromonomer (DD-2V) with some SiH-functionalized siloxanes (Scheme 4). 

REGIO- AND STEREOSELECTIVE INTRAMOLECULAR HYDRO-SILYLATION OF a-HYDROXY ENOL ETHERS 2,3-syn-2-METHOXY-METHOXY-1,3-NONANEDIOL... 

Benzyl-(diethyl-hydro-silyl)-methyl-E18, 739 (Imin-Hydrosilylier.)... 

Bis-[dimethyl-hydro-silyl]-amino)-dimethylamino-phenyl- XIII/3b, 287... 

R1 R2 (in catalyst) Temp (nC), Time (h) (hydro-silylation step) Trichlorosilanes Config. of Product 10 ee (%) MS0 (c, solvent)... 

It was described earlier that the diselenide 2 acted as chiral ligand for the Rh(I)-catalyzed asymmetric hydrosilylation of unfunctionalized alkyl aryl ketones with diphenylsilane in tetrahydrofuran [6]. When the reaction was carried out in methanol as solvent, it gave directly a chiral alcohol, not a hydro-silylated product [7] (Scheme 5). 

Hydrosilylation can also be initiated by a free-radical mechanism (227—229). A photochemical route uses photosensitizers such as peresters to generate radicals in the system. Unfortunately, the reaction is quite sluggish. In several apphcations, radiation is used in combination with platinum and an inhibitor to cure via hydro silylation (230—232). The inhibitor is either destroyed or deactivated by uv radiation. 

An enamine (55) reacts with trichlorosilane in acetonitrile in the absence of catalyst to give a hydro-silylated product (56 equation 45). The regiochemistry is opposite to the standard pattern, the silyl group attaching itself to the more-hindered carbon. ... 

Enol silyl ethers undergo aldol reactions with aldehydes, acetals and their equivalents with the aid of a Lewis acid catalyst. These reactions are discussed in Volumes 2-4. Enol silyl ethers prepared by hydro-silylation of a, 3-unsaturated ketones with a rhodium catalyst can be used for aldol reactions with aldehydes or ketones in situ under neutral conditions (equation 60)." ... 

In addition, aUcynyl groups not only inhibit thermally inducted depolymerization, they can also be functionalized by, for example, hydroboration, hydro-silylation, or by attaching transition metal complex fragments. Accordingly, nnits provide an access to multicomponent ceramics. For example, Corriu et al. reported that [SiR2C=C-C=C] are precursors with interpenetrating networks to... 

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