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Disilylations

TMS triflate [27607-77-8] is an extremely powerful sdylating agent for most active hydrogens. It surpasses the sdylating potential of TMCS by a factor of nearly 10. It readily converts 1,2- and 1,3-diketones into disilylated dienes (7). [Pg.71]

A variable pressure oil pump was used in this distillation. Approximately 10 g of a volatile component, consisting mostly of hexamethyl-disiloxane, was obtained at room temperature (15 (in) before the forerun. The forerun contained the desired product and mineral oil from the n-butyllithium solution. The pot residue was about 5 g. The submitters find the disilyl compound thus obtained is contaminated with a trace amount of mineral oil and 4-6% of a vinylsilane, probably 2-methyl-l-trimethylsiloxy-3-trimethylsilyl-2-propene. This impurity becomes quite significant if the reaction medium is less polar than the one described (e.g., too much hexane from n-butyllithium is allowed to remain behind). The spectral properties of the desired product... [Pg.63]

A similar procedure has been employed to silylate the dianion of 3-methyl-3-buten-2-ol (67% yield).In systems where such internal activation is not possible (e.g. 2-raethyl-2-cyclohexen-l-o1), dianion formation can be performed in hexane to give a 75% yield of the corresponding disilyl compound. [Pg.65]

The most common use of the Paal-Knorr condensation begins with a 1,4-diketone and yields a 2,5-disubstituted furan. This method has been used to produce dialkyl and disilyl furans however, the most popular use of this strategy is for the production of 2,5-diaryl furans. In addition to their utility as synthetic intermediates, these compounds are under investigation for novel electronic and pharmaceutical applications. [Pg.169]

Recently, good yields of glyphosate have been reported after hydrolysis using tris-trimethylsilyl phosphite in a similar sequence with 48 to generate the disilyl phosphonate triester intermediate 50 (S3). [Pg.27]

Cyclohexanones have been converted to 8-chloroquinolines through a series of reactions involving imination, a-alkylation with Af,N-disilyl protected oa-bromoamines, transimination, a-chlorination of the resulting bicyclic imines, dehydrochlorination and dehydrogenation <96T(52)3705>. A short, high yielding one-pot synthesis of acenaptho(l,2-b)benzoquinolines... [Pg.231]

Hydride species were also formed in the dehydrogenative coupling of hydrosilanes with DMF [45]. The catalytic system is applicable to tertiary silanes, which are known to be difficult to be converted into disiloxanes (Fig. 17). The catalytic reaction pathway involves the intermediacy of a hydrido(disilyl)iron complex... [Pg.151]

These reactions presumably proceed by catalytic cycles in which the carbonyl component is silylated. The silyl ether can then act as a nucleophile, and an oxonium ion is generated by elimination of a disilyl ether. The reduction of the oxonium ion regenerates the silyl cation, which can continue the catalytic cycle. [Pg.428]

A study aimed at optimizing yields in this reaction found that carbinol formation was a major competing process if the reaction was not carried out in such a way that all of the lithium compound was consumed prior to hydrolysis.113 Any excess lithium reagent that is present reacts extremely rapidly with the ketone as it is formed by hydrolysis. Another way to avoid the problem of carbinol formation is to quench the reaction mixture with trimethylsilyl chloride.114 This procedure generates the disilyl acetal, which is stable until hydrolysis. [Pg.645]

Conjugate addition can also be carried out by fluoride-mediated disilylation. A variety of a, (3-unsaturated esters and amides have been found to undergo this reaction.136... [Pg.831]

The behavior of the Si—P 7r-bond toward a G=C triple bond was examined in the case of 15a by employing differently substituted alkynes.14 It appeared that 15a does not react with dialkyl, diaryl-, or disilyl-substi-tuted alkynes at 110°C even cyclooctyne, usually a very reactive alkyne, does not react. However, when 15a was stirred with phenylacetylene at 80°C in toluene, the C—H insertion product 24 was isolated as colorless crystals (Eq. 9).14 Its molecular structure has been elucidated by singlecrystal X-ray diffraction (Fig. 9). [Pg.212]

The chemistry of silylene-metal complexes has developed in quite another direction, however, from reactions of disilyl-metal complexes, leading to complexes of otherwise unstable disilenes such as Me2Si=SiMe2. Molybdenum and tungsten complexes have been particularly well investigated by Berry and co-workers,103 and platinum complexes have also been isolated.104 Readers interested in this field are directed to a 1992 review of silylene, silene, and disilene-metal complexes.105... [Pg.269]

A similar dichotomy was observed in the titanium catalyzed polymerization of primary silanes coupled to the hydrogenation of norbornene (20). At low catalyst concentration (ca. 0.004H), essentially complete conversion of norbornene to an equimolar mixture of norbornane and bis-phenylsilyl- (and/or 1,2-diphenyl-disilyl)norbornane was observed. Under these conditions no evidence for reduction of titanium was obtained. At higher catalyst concentrations (> 0.02M) rapid reduction of the dimethyltitanocene to J, and 2 occurs and the catalytic reaction produces mainly polysilane (DPn ca. 10) and norbornane in ca. 80 per cent yields, and silylated norbornanes in about 20 per cent yield. [Pg.98]

Platinum(O) phosphine complexes undergo a variety of oxidative addition reactions with compounds containing Group 14 elements. These reactions are of widespread interest because similar processes are probably involved in the catalysis by platinum complexes of reactions such as the hydrosilation of alkenes and the disilylation of dienes and alkenes. [Pg.678]

Thermolysis of 12 with frans-cinnamaldehyde afforded the insertion compound 19, formed through the di-insertion of two carbonyl ligands into the C—Si bond of 12. The reaction of 12 with fumaronitrile yielded the cyclization product 20. X-ray study revealed 20 to be a cyclization product which contains two types of disilyl moieties, imino and N,N-bis(silyl)amino, which are connected by a five-membered ring. [Pg.67]

See Dioxygen difluoride Various materials Disilyl oxide... [Pg.1405]

Me(Ph)SiCl2 reacts with dimethyl phosphonate in a 1 1-mixture at 100°C to the O.O-disilylated phosphonate. In contrast to this observation the O-alkyl O-silyl phosphonate is formed solely by reaction of both compounds in acetonitrile at 80°C (line 7,8). An excess of the corresponding phosphonate as polar solvent leads to the mixed ester 2 only. The excess of the dialkyl phosphonate is removed from the mixture by vacuum distillation (line 9). [Pg.76]

Dialkoxydichloro silanes exhibit a higher nucleophilicity compared to the chlorosilanes described before. Diethoxysilyl-bis(0-alkyl)phosphonates of type 8 are formed in 90% yield besides 10% of disilylated phosphonates in the reaction of dialkyl phosphonates with dichlorodiethoxy silanes at 50-80°C. [Pg.76]

The silylation of benzylic G-H bonds is achieved by using Ru3(GO)12 catalyst in the presence of norbornene as a hydrogen acceptor.145 The reaction of 2-(2,6-dimethylphenyl)pyridine with triethylsilane in the presence of Ru3(CO)i2 catalyst and norbornene affords mono- and disilylation products in 30% and 55% yields, respectively (Equation (106)). The reaction of 2-(2-tolyl)pyridine shows that the silylation of the aromatic C-H bond is more facile than that of the benzylic C-H bond. [Pg.240]

The rhodium-catalyzed cyclization/hydrosilylation of internal diyne proceeds efficiently with high stereoselectivity (Scheme 106). However, terminal diynes show low reactivity to rhodium cationic complexes. Tolerance of functionalities seems to be equivalent between the rhodium and platinum catalysts. The bulkiness of the hydrosilane used is very important for the regioselectivity of the rhodium-catalyzed cyclization/hydrosilylation. For example, less-hindered dimethylethylsilane gives disilylated diene without cyclization (resulting in the double hydrosilylation of the two alkynes), and /-butyldimethylsilane leads to the formation of cyclotrimerization compound. [Pg.352]

The results indicate that the formation of long-lived trimethyl substituted silyl cations, in the presence of aromatic solvents, as claimed by Lambert et al.95 is not feasible under these conditions. Persistent silicenium ions require sterically more shielding substituents at silicon or hypercoordinative stabilization.96 98 13C and 29Si NMR chemical shifts were calculated for a series of disilylated arenium ions 85 using density functional theory (DFT). The calculations predict consistently the unsaturated carbon atoms to be too deshielded by 8-15 ppm. Applying an empirical correction, the deviation between experiment and theory was reduced to -0.4 to 9 ppm, and the 13C NMR chemical shift of the highly diagnostic cipso is reproduced by the calculations (Ad = -3.8 to 2.7 ppm).99... [Pg.151]

Selective silylation of polychloromethanes using reactive metal electrodes such as zinc and magnesium has also been reported as shown in Scheme 37 [76, 77]. The electroreduction of carbon tetrachloride and chloroform in the presence of chlorotrimethylsilane affords the monosilylated and disilylated products. The product selectivity seems to depend upon the electrode material. [Pg.83]

Selenoaldehydes,2 In the presence of 5-10 mole% of butyllithium, this disilyl selenide converts aldehydes into selenoaldehydes with formation of the disiloxane [(CH,)3SiOSi(CH3),]. The active reagent is presumed to be lithium trimethylsilyl-selenide, (CH3)3SiSeLi, which can be regenerated by a Peterson-type elimination (equation I). [Pg.51]

Aldehydes can be converted into thioaldehydes by a similar reaction with bis(trimethylsilyl) sulfide catalyzed by BuLi (equation II). This disilyl sulfide has been used indirectly for conversion of aldehydes into thioaldehydes via boron trisulfide (11, 63). [Pg.51]


See other pages where Disilylations is mentioned: [Pg.519]    [Pg.275]    [Pg.155]    [Pg.216]    [Pg.108]    [Pg.109]    [Pg.247]    [Pg.248]    [Pg.154]    [Pg.20]    [Pg.218]    [Pg.388]    [Pg.1261]    [Pg.1695]    [Pg.1695]    [Pg.1695]    [Pg.76]    [Pg.67]    [Pg.29]    [Pg.606]    [Pg.105]    [Pg.324]    [Pg.368]    [Pg.83]    [Pg.422]   


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1.3- Disilyl ethers

1.4- Disilyl-2-alkenes

1.4- Disilyl-2-butenes

1.4- Disilylation

3.7- Dioxabicyclo octane use of disilyl enol ether

Butenolides use of disilyl enol ether

Disilyl

Disilyl cations

Disilyl phosphines

Disilyl selenide

Disilyl sulfide

Disilyl thioketene

Disilyl-substituted compounds

Enol ethers disilyl

Glutarates disilyl ketene acetals

Hydrosilylation and Disilylation

Ketene disilyl acetals

Succinic acid disilyl ketene acetals

Succinic anhydride disilyl enol ethers

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