- Continuous-flow Si-H functionalizations of hydrosilanesviasequential organolithium reactions catalyzed by potassiumtert-butoxide
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We herein report an atom-economic flow approach to the selective and sequential mono-, di-, and tri-functionalizations of unactivated hydrosilanesviaserial organolithium reactions catalyzed by earth-abundant metal compounds. Based on the screening of various additives, we found that catalytic potassiumtert-butoxide (t-BuOK) facilitates the rapid reaction of organolithiums with hydrosilanes. Using a flow microreactor system, various organolithiums bearing functional groups were efficiently generatedin situunder mild conditions and consecutively reacted with hydrosilanes in the presence oft-BuOK within 1 min. We also successfully conducted the di-funtionalizations of dihydrosilane by sequential organolithium reactions, extending to a gram-scale-synthesis. Finally, the combinatorial functionalizations of trihydrosilane were achieved to give every conceivable combination of tetrasubstituted organosilane libraries based on a precise reaction control using an integrated one-flow system.
- Lee, Hyune-Jea,Kwak, Changmo,Kim, Dong-Pyo,Kim, Heejin
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supporting information
p. 1193 - 1199
(2021/02/26)
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- Silylation of Aryl Chlorides by Bimetallic Catalysis of Palladium and Gold on Alloy Nanoparticles
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Supported palladium-gold alloy-catalyzed cross-coupling of aryl chlorides and hydrosilanes enabled the selective formation of aryl-silicon bonds. Whereas a monometallic palladium catalyst predominantly promoted the hydrodechlorination of aryl chlorides and gold nanoparticles showed no catalytic activity, gold-rich palladium-gold alloy nanoparticles efficiently catalyzed the title reaction to give arylsilanes with high selectivity. A wide array of aryl chlorides and hydrosilanes participated in the heterogeneously-catalyzed reaction to furnish the corresponding arylsilanes in 34–80% yields. A detailed mechanistic investigation revealed that palladium and gold atoms on the surface of alloy nanoparticles independently functioned as active sites for the formation of aryl nucleophiles and silyl electrophiles, respectively, which indicates that palladium and gold atoms on alloy nanoparticles work together to enable the selective formation of aryl-silicon bonds. (Figure presented.).
- Miura, Hiroki,Masaki, Yosuke,Fukuta, Yohei,Shishido, Tetsuya
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p. 2642 - 2650
(2020/04/22)
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- Reactivity of Hypervalent Species: Reactions of Anionic Penta-Coordinated Silicon Complexes towards Nucleophiles
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The reactivity of anionic penta-coordinated silicon complexes 4-O)2>-Na+ 1 with nucleophilic reagents has been studied. 1 can be reduced to organosilanes RSiH3 by metallic hydrides.Reactions with an excess of Grignard or organolithium reagents (R'MgX or R'Li) gave tetraorganosilanes RSiR'3.When only two molar equivalents of Grignard reagents (R'MgX) or lithium reagents (R'Li) are added to complexs 1 functional silanes RR'2SiX can be prepared.
- Boudin, Alain,Cerveau, Genevieve,Chuit, Claude,Corriu, Robert J. P.
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p. 101 - 106
(2007/10/02)
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- Pentacoordinate silicon complexes, the process for their preparation and their application to the preparation of organosilanes
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The present invention relates to new pentacoordinate silicon complexes, the process for their preparation and their application to the preparation of organosilanes. The pentacoordinate silicon complexes according to the invention correspond to the general formula I: STR1 in which: R denotes an alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, aralkynyl or alkylaryl radical in which the aliphatic fragments are linear, branched or cyclic and contain from 1 to 20 carbon atoms, A represents an alkali metal or alkaline earth metal, with the proviso however that A represents neither sodium nor potassium when R is a phenyl radical, and n=1 or 2.
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