14595-77-8Relevant academic research and scientific papers
Photochemistry of benzene
Sakurai, Hideki,Yoshida, Hitoaki,Kira, Mitsuo
, p. 1780 - 1781 (1985)
Irradiation of benzene (trisylbenzene) (1) gave mainly -p-trimethylsilylbenzene (2) and benzene (3); a free radical mechanism is proposed.
Electrochemical Synthesis of (α-Halobenzyl)silanes and Benzyl Disilanes
Fry, Albert J.,Touster, Jonathan
, p. 4829 - 4832 (1989)
Electrochemical reduction of a series of substituted benzal chlorides (4) in dimethylformamide containing excess chlorotrimetylsilane affords (α-chlorobenzyl)trimetylsilanes (5) or benzal (geminal) disilanes (6), depending upon experimental conditions.Benzal bromide (13) is reducted to (α-bromobenzyl)trimetylsilane (14) cleanly and in high yield without subsequent conversion to the geminal disilane 6a, apparently because of electrode passivation by bromide ion.The reaction are conveniently carried out at constant current in an undivided cell containing a stainless steel cathode and sacrificial magnesium anode.
Stereoselective peterson olefinations from bench-stable reagents and N-phenyl imines
Das, Manas,Manvar, Atul,Jacolot, Ma?wenn,Blangetti, Marco,Jones, Roderick C.,O'Shea, Donal F.
supporting information, p. 8737 - 8740 (2015/06/08)
The synthesis of bench-stable α,α-bis(trimethylsilyl)toluenes and tris(trimethylsilyl)methane is described and their use in stereoselective Peterson olefinations has been achieved with a wide substrate scope. Product stereoselectivity was poor with carbonyl electrophiles (E/Z ～1:1 to 4:1) though this was significantly improved by employing the corresponding substituted N-benzylideneaniline (up to 99:1) as an alternative electrophile. The olefination byproduct was identified as N,N-bis(trimethylsilyl)aniline and could be easily separated from product by aqueous acid extraction. Evidence for an autocatalytic cycle has been obtained.
General Ambient Temperature Benzylic Metalations Using Mixed-Metal Li/K-TMP Amide
Manvar, Atul,Fleming, Patricia,O'Shea, Donal F.
, p. 8727 - 8738 (2015/09/15)
Highly regioselective benzylic metalations in hydrocarbon solvent have been achieved at rt and 0 °C using a mixed-metal Li/K-TMP amide comprised of KOtBu, BuLi, and 2,2,6,6,-tetramethylpiperidine (TMP(H)). Mixing of KOtBu, BuLi, and TMP(H) in heptane gave a solution of the base mixture which when used in deuterium labeling experiments confirmed the requirement of the three reagent components for both reactivity and selectivity. The reaction protocol is operationally straightforward and found to be applicable to a broad range of substrates. Upon generation of the metalated products, they are reacted in heptane at ambient temperature in a variety of synthetically useful ways. Illustrated examples include generation of the benzyltrimethylsilanes and α,α-bis(trimethylsilyl)toluenes reagents, which are bench-stable surrogates of benzyl anions and α-silyl carbanions utilized for nucleophilic addition and Peterson olefination reactions. Direct C-C couplings mediated by 1,2-dibromoethane provided entries into bibenzyls and [2.2]metacyclophanes. Comparison of reaction outcomes with the same reactions carried out in THF at -78 °C showed no negative effects for conducting the reactions under these milder more user-friendly conditions.
Polychlorinated materials as a source of polyanionic synthons
Guijarro, Albert,Yus, Miguel
, p. 1797 - 1810 (2007/10/03)
The reaction of dichloromethane (1a) or dichlorodideuteriomethane (1b) with an excess of lithium powder (1:7 molar ratio) and a catalytic amount of DTBB (5 mol%) in the presence of a carbonyl compound 2 (1:2 molar ratio) in THF at -40°C yields, after hydrolysis, the corresponding 1,3-diols 3 in moderate yields. The process is applied to other gem-dichlorinated materials such as 7,7-dichloro [4.1.0]heptane (4), 1,1-dichlorotetramethylcyclopropane (7) and dichloromethyl methyl ether (10), using pivalaldehyde as electrophile. Starting from 1,1,1-trichlorinated compounds or tetrachloromethane (14) and using chlorotrimethylsilane as electrophile at temperatures ranging between -80 and -90°C, the corresponding polysilylated compounds 15-17 are prepared applying the mentioned methodology.
Novel Syntheses of 1,2-Diarylacetylenes and α-Silylalcohols from Acylsilanes Mediated by Ytterbium Metal
Taniguchi, Yuki,Fujii, Nobuto,Makioka, Yoshikazu,Takaki, Ken,Fujiwara, Yuzo
, p. 1165 - 1168 (2007/10/02)
Aromatic acylsilanes such as benzoyltrimethylsilane react with ytterbium metal to give symmetrical 1,2-diarylacetylenes in good yields.Aliphatic acylsilanes are reduced with lanthanoid reagents as Yb metal and SmI2 to afford α-silylalcohols.
Ion Pair Carbon Acidities of Some Silanes in Tetrahydrofuran
Streitwieser, Andrew,Xie, Linfeng,Wang, Peng,Bachrach, Steven M.
, p. 1778 - 1784 (2007/10/02)
The relative solvent-separated ion pair (SSIP) lithium acidity (pKLi/THF) and contact ion pair (CIP) cesium acidity (pKCs/THF) were obtained for 9-fluorenyltrimethylsilane (1) (21.3, 21.6, respectively) and 9-fluorenyl-tert-butyldimethylsilane (2) (20.3, 20.6, respectively) in THF.Values for pKCs/THF were determined at 25 deg C for (p-biphenylylmethyl)-tert-butyldimethylsilane (3), 35.4, benzyltrimethylsilane (4), 37.5, α,α-bis(trimethylsilyl)toluene (5), 34.1, 2-(trimethylsilyl)-1,3-dithiane (6), 33.5, (trimethylsilyl)acetonitrile (7), 28.8, and tris(trimethylsilyl)methane (8), 36.8.Some thermodynamic parameters were determined by measurements at other temperatures, and some ionic acidities (pK(FI)) were determined by conductivity studies.Carbanion stabilization by these silyl substituents varies from about 1 to over 3 pK units in different systems. 9,9-Bis(trimethylsilyl)fluorene (9) was found to undergo silyl transfer on treatment with various carbanions, but this reaction is slower than proton transfer.
Two new strongly basic systems prepared by activation of n-butyllithium with organopotassium compounds
Scott, Frederick,Hamese, Augustine M.,Raubenheimer, Helgard G.
, p. C40 - C42 (2007/10/02)
Treatment of n-butyllithium with potassium cyclopentadienide or potassium naphthalenide yields a strongly basic system.The activation of n-butyllithium with potassium cyclopentadienide also enhances its reactivity in nucleophilic substitution reactions.
Main Group Conjugated Organic Anion Chemistry. 3. Application of Magnesium-Anthracene Compounds in the Synthesis of Grignard Reagents
Harvey, Stephen,Junk, Peter C.,Raston, Colin L.,Salem, Geoffrey
, p. 3134 - 3140 (2007/10/02)
Reaction of magnesium-arene compounds, , 1, and some silylanthracene, and/or tertiary amine analogues, with benzylic and allylic chlorides or bromides, and (Me3Si)3CCl, afford Grignard reagents, RMgX, in modest to high yield for chlorides and negligible to high yield for the bromides, in THF, toluene, and hexane at -10 to 20 deg C.Novel benzylic-type Grignard reagents prepared in high yield include those of 9-(chloromethyl)anthracene, 2-(chloromethyl)pyridine and 8-(chloro(or bromo)methyl)quinoline, and poly-Grignard reagents derived from 1,8-bis(chloromethyl)naphthalene, 2,2'-bis(chloromethyl)-1,1'-binaphthyl, and 1,3,5,-tris(chloro(or bromo)methyl)benzene.Grignard reagent formation occurs via electron-transfer reactions.Aryl and alkyl halides yield mainly products derived from addition of the halide across the 9,10-positions of the anthracenes, via nucleophilic substitution or collapse of a diradical cage 2+, (anthracene)-anion radical, RX-anion radical.>
1,n-TRIORGANOSILYL MIGRATIONS IN THE REARRANGEMENTS OF SILYL-SUBSTITUTED ORGANOLITHIUM COMPOUNDS
Eisch, John J.,Tsai, Miin-Rong
, p. 5 - 24 (2007/10/02)
Under the agency of the potent lithiating agent, n-butyllithium in TMEDA, an array of organosilanes was found to undergo 1,n-silyl rearangements via carbanionic intermediates.Unambiguous 1,2-, 1,3- and 1,4-silyl shifts were unconvered in 1-trimethylsilyl-
