Convenient synthesis of alkoxyhalosilanes from hydrosilanes

The photochemistry of 3,4-dimethyl-1,1-diphenylsilacyclopent-3-ene (2), a potential precursor to diphenylsilylene (SiPh 2 ), has been studied in hydrocarbon and methanol solution by steady state and laser flash photolysis techniques. The results are consistent with the formation of three major photoproducts: SiPh 2 (ca. 20%), 2,3-dimethyl-1,3-butadiene (DMB; ca. 20%), and 2-methyl-2-(1-methylethenyl)-1,1-diphenylsilirane (9; ca. 75%), the product of formal photochemical (1,3)-sigmatropic rearrangement of 2. Attempts to detect the silylene by laser flash photolysis were unsuccessful, but the vinylsilirane could be easily detected as a long-lived transient exhibiting λ max = 285 nm and lifetime τ = 1.3 s in hexane at 25 • C. The same spectrum is observed in neat methanol solution, where the lifetime of the species is shortened to τ = 36 ms and it is quenched by sodium methoxide and methanesulfonic acid with absolute rate constants of k MeO -= 2.0 × 10 6 M −1 s −1 and k H+ = 2.6 × 10 3 M −1 s −1 , respectively. The photochemistry of 2 is compared to that of the corresponding germanium homologue (1), whose photolysis in solution has been previously shown to afford diphenylgermylene and DMB cleanly and in high yields. The corresponding vinylgermirane (11a), though not detectable as a primary photoproduct from 1 in solution, is the exclusive product of photolysis of 1 in a 3-methylpentane glass at 78 K, where it exhibits an essentially identical UV/vis spectrum to that of 9. The rate constant for its unimolecular thermal isomerization to regenerate 1 is three orders of magnitude larger than that of the corresponding process in the homologous vinylsilirane (9) in hydrocarbon solution at 25 • C.

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“…40%). The two compounds were identified by comparison of their 1 H NMR spectra to the reported spectra [46] and by GC/MS. …”

Section: Synthesis Of Methoxydiphenylsilane (5)mentioning

confidence: 99%

The photochemistry of a potential diphenylsilylene precursor. Time-resolved spectroscopic studies of the reactivity of a transient vinylsilirane

et al. 2006

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“…The starting alkoxychlorosilanes were prepared from hydrosilanes according to the literature procedure (Scheme 5, Table 3) [9]. Data for newly prepared alkoxychlorosilanes follow.…”

Section: Preparation Of Alkoxychlorosilanesmentioning

confidence: 99%

“…: colorless oil; bp 110°C, 1 mmHg; GC-MS m/z 276 (M + ), 233 (M + -iPr), 217 (M + -OiPr); 1 H NMR (d in CDCl 3 ) 1.26 (d, J = 5 9. Hz, 6H, CHMe 2 ), 4.34 (sept, J = 5 3.…”

mentioning

confidence: 99%

“…43 g, 0.89 mmol; 56%) as a colorless solid: mp 127-130°C; MS m/z 482 (M + ), 439 (M + -iPr), 405 (M + -Ph), 241 (M + -SiPh 2 OiPr); 1 H NMR (d in CDCl 3 ) 1.10 (d, J = 5 9. Hz, 12H, CHMe 2 ), 4.13 (sept, J = 5 9.…”

mentioning

confidence: 99%

“…Hz, 12H, CHMe 2 ), 4.13 (sept, J = 5 9. Hz, 2H, CHMe 2 ), 12H, Ph); (m, 8H, Ph); 13 C NMR (d in CDCl3) 25.75 (Me), 67.17 (CMe 2 ), 127.60, 129.43 (Ph CH), 134.10 (Ph ipso-C), 135.35 (Ph CH).…”

mentioning

confidence: 99%

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Electrochemical reduction of alkoxychlorosilanes for Si–Si bond formation

Ohshita

Hino

Iwawaki

et al. 2009

Journal of Electroanalytical Chemistry

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Copper‐Catalyzed Reduction of Alkyl Triflates and Iodides: An Efficient Method for the Deoxygenation of Primary and Secondary Alcohols

2013

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We describe an effective method for catalytic reduction of 18 alkyl sulfonates, and 18 and 28 iodides in the presence of a wide range of functional groups. This Cucatalyzed reaction provides a means for the effective deoxygenation of alcohols, as demonstrated by the highly selective reduction of 18 alcohols using a triflation/reduction sequence. A preliminary study of the reaction mechanism suggests that the reduction does not involve free-radical intermediates.Scheme 1. Cu-catalyzed approach to the deoxygenation of alcohols.

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Convenient synthesis of alkoxyhalosilanes from hydrosilanes

Cited by 32 publications

References 10 publications

The photochemistry of a potential diphenylsilylene precursor. Time-resolved spectroscopic studies of the reactivity of a transient vinylsilirane

The photochemistry of a potential diphenylsilylene precursor. Time-resolved spectroscopic studies of the reactivity of a transient vinylsilirane

Electrochemical reduction of alkoxychlorosilanes for Si–Si bond formation

Copper‐Catalyzed Reduction of Alkyl Triflates and Iodides: An Efficient Method for the Deoxygenation of Primary and Secondary Alcohols

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