13688-68-1Relevant articles and documents
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Coutant,Levy
, p. 175 (1967)
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THE CHEMISTRY OF SILOLES. SYNTHESIS AND REACTIONS OF η6-CHROMIUM TRICARBONYL
Ishikawa, Mitsuo,Tabohashi, Tatsuru
, p. C4 - C6 (1984)
η6-chromium tricarbonyl (II) was prepared by the reaction of 1-methyl-1-(trimethylsilyl)dibenzosilole with chromium hexacarbonyl.The reaction of II with methyllithium in THF gave η6-(1,1-dimethyldibenzosilacyclopentadiene)chromium tricarbonyl.Similar reaction of II with butyllithium, followed by oxidation, gave 1-butyl-1-methyldibenzosilole and 1,1-dibutyldibenzosilole, while reaction with (methyldiphenylsilyl)lithium under similar conditions afforded 1-methyl-4-(methyldiphenylsilyl)-1-(trimethylsilyl)dibenzosilole.
Synthesis and characterization of dibenzannulated silole dianions. The 1,1-dilithiosilafluorene and 1,1'-dilithiobis(silafluorene) dianions
Choi,Boudjouk
, p. 6685 - 6688 (2000)
Stirring of 1,1-dichloro-SiFl (1), (SiFl, silafluorene) in THF with excess lithium for 1 h gave a dark green solution of 1,1-dilithio-SiFl (2) in high yield. The dark red solution of the intermediate 1,1'-dilithio-(SiFl)2 (3) was also observed from this reaction within 10 min. Treatment of 2 with excess trimethylchlorosilane gave the 1,1-bis(trimethylsilyl)-SiFl derivative (4) in 95% yield. Treatment of the dark red solution of 3 and 2 with excess methyliodide gave the 1,1'-dimethyl-bis(SiFl) (5) and 1,1-dimethyl-SiFl (6) derivatives in a 4:1 ratio. The upfield locations of the 29Si resonances of dianions 2 and 3 (-1.09 ppm and -39.25 ppm, respectively) are consistent with π-electron localization on the silicon atoms. (C) 2000 Elsevier Science Ltd.
UNEXPECTED BEHAVIOR OF SILOLES TOWARD ORGANOLITHIUM REAGENTS
Ishikawa, Mitsuo,Nishimura, Kunio,Sugisawa, Hiroshi,Kumada, Makoto
, p. C21 - C24 (1981)
The reaction of 5-trimethylsilyl-5-methyldibenzosilole (I) with an excess of methyllithium in THF afforded 5,5-dimethyldibenzosilole (II) in quantitative yield.Treatment of I with an excess of butyllithium gave 5,5-dibutyldibenzosilole (III) quantitatively.Similar treatment of II with butyllithium in THF at room temperature gave III in almost quantitative yield, while treatment of III with methyllithium at reflux temperature gave II and 5-butyl-5-methyldibenzosilole in 10 and 40percent yield, in addition to 37percent of the starting III. 1,2,5-Tris(trimethylsilyl)-1-methyl-3,4-diphenylsilole also reacted with methyllithium to give 1,1-dimethyl-2,2,5-tris(trimethylsilyl)-3,4-diphenyl-1-silacyclopent-3-ene and 1,1-dimethyl-2,5-bis(trimethylsilyl)-3,4-diphenylsilole in 70 and 7percent yield.A five-coordinate silicon compound is proposed as an intermediate.
A Catalytic SEAr Approach to Dibenzosiloles Functionalized at Both Benzene Cores
Omann, Lukas,Oestreich, Martin
, p. 10276 - 10279 (2015)
A general procedure for the catalytic preparation of dibenzosiloles functionalized at one or both benzene rings starting from readily available ortho-silylated biphenyls is reported. This method provides rapid access to silole building blocks substituted with chlorine atoms at both phenylene groups, thereby allowing catalytic access to directly polymerizable dibenzosiloles. Moreover, it is shown that, despite the involvement of highly electrophilic intermediates, a considerable range of Lewis-basic, for example, oxygen- and nitrogen-containing, functional groups is tolerated. The mechanism of this intramolecular electrophilic aromatic substitution (SEAr) proceeds through a sulfur-stabilized silicon cation, generated catalytically from the hydrosilane precursor.
Me3SiSiMe2(OnBu): a disilane reagent for the synthesis of diverse silacyclesviaBrook- And retro-Brook-type rearrangement
Xu, Yankun,Xu, Weiwei,Chen, Xinyang,Luo, Xiai,Lu, Haiyan,Zhang, Minghao,Yang, Xiumei,Deng, Guobo,Liang, Yun,Yang, Yuan
, p. 11756 - 11761 (2021/09/22)
Herein, a readily available disilane Me3SiSiMe2(OnBu) has been developed for the synthesis of diverse silacyclesviaBrook- and retro-Brook-type rearrangement. This protocol enables the incorporation of a silylene into different starting materials, including acrylamides, alkene-tethered 2-(2-iodophenyl)-1H-indoles, and 2-iodobiaryls,viathe cleavage of Si-Si, Si-C, and Si-O bonds, leading to the formation of spirobenzosiloles, fused benzosiloles, and π-conjugated dibenzosiloles in moderate to good yields. Preliminary mechanistic studies indicate that this transformation is realized by successive palladium-catalyzed bis-silylation and Brook- and retro-Brook-type rearrangement of silane-tethered silanols.
Aromatic Metamorphosis of Thiophenes by Means of Desulfurative Dilithiation
Kaga, Atsushi,Iida, Hirokazu,Tsuchiya, Shun,Saito, Hayate,Nakano, Koji,Yorimitsu, Hideki
supporting information, p. 4567 - 4572 (2021/02/12)
A new mode of aromatic metamorphosis has been developed, which allows thiophenes and their benzo-fused derivatives to be converted to a variety of exotic heteroles. This transformation involves 1) the efficient generation of key 1,4-dianions by means of desulfurative dilithiation with lithium powder and 2) the subsequent trapping of the dianions with heteroatom electrophiles in a one-pot manner. Via the desulfurative dilithiation, the sulfur atoms of thiophenes are replaced also with a carbon–carbon double bond or a 1,2-phenylene for the construction of benzene rings.