35192-37-1

Upstream product

• 109-72-8 n-butyllithium 
• 121004-58-8 tert-butoxy(methyl)diphenylsilane 
• 693-03-8 n-butyl magnesium bromide 
• 144-79-6 chloromethyldiphenylsilane 
• 542-69-8 1-iodo-butane 
• 776-76-1 methyldiphenylsilane 
• 694-53-1 phenylsilane 
• 917-54-4 methyllithium 
• 591-51-5 phenyllithium 
• 18666-25-6 benzyl methyl diphenylsilane 

Relevant academic research and scientific papers

Continuous-flow Si-H functionalizations of hydrosilanesviasequential organolithium reactions catalyzed by potassiumtert-butoxide

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.

Thermal, Catalytic Conversion of Alkanes to Linear Aldehydes and Linear Amines

Alkanes, the main constituents of petroleum, are attractive feedstocks for producing value-added chemicals. Linear aldehydes and amines are two of the most important building blocks in the chemical industry. To date, there have been no effective methods for directly converting n-alkanes to linear aldehydes and linear amines. Here, we report a molecular dual-catalyst system for production of linear aldehydes via regioselective carbonylation of n-alkanes. The system is comprised of a pincer iridium catalyst for transfer-dehydrogenation of the alkane using t-butylethylene or ethylene as a hydrogen acceptor working sequentially with a rhodium catalyst for olefin isomerization-hydroformylation with syngas. The system exhibits high regioselectivity for linear aldehydes and gives high catalytic turnover numbers when using ethylene as the acceptor. In addition, the direct conversion of light alkanes, n-pentane and n-hexane, to siloxy-terminated alkyl aldehydes through a sequence of Ir/Fe-catalyzed alkane silylation and Ir/Rh-catalyzed alkane carbonylation, is described. Finally, the Ir/Rh dual-catalyst strategy has been successfully applied to regioselective alkane aminomethylation to form linear alkyl amines.

Selective Si?C(sp3) Bond Cleavage in (Aminomethyl)silanes by Carbanionic Nucleophiles and Its Stereochemical Course

Selective cleavage of a silicon–carbon bond in tetraorganosilanes is still a great challenge. A new type of Si?C(sp3) bond cleavage in bench-stable (aminomethyl)silanes with common organolithium reagents as nucleophiles has now been identified. Suitable leaving groups are benzyl, allyl, and phenylthiomethyl groups. A β-donor function and polar solvents are essential for the reaction. Simple switching between α-deprotonation and substitution is possible through slight modifications of the reaction conditions. The stereochemical course of the reaction was elucidated by using a silicon-chiral benzylsilane. The new transformation proceeds stereospecifically with inversion of configuration and can be used for the targeted synthesis of enantiomerically pure tetraorganosilanes, which are otherwise difficult to access. Quantum chemical calculations provided insight into the mechanism of the new substitution.

Direct synthesis of alkylsilanes by platinum-catalyzed coupling of hydrosilanes and iodoalkanes

Alkyl iodides and tertiary silanes were successfully coupled with good functional group tolerance using a Pt(P(tBu)3)2/(iPr) 2EtN/CH3CN system. The utility of the methodology is demonstrated by the synthesis of silafluofen, a Si-containing insecticide. This journal is The Royal Society of Chemistry.

Copper-catalyzed arylation of chlorosilanes with grignard reagents

Nucleophilic substitution reactions of chlorosilanes with aryl Grignard reagents take place efficiently in the presence of copper(I) iodide to afford tetraorganosilanes.

Die Chemie von Silylenoiden: Synthese und Reaktivitaet von (Alkoxysilyl)lithiumverbindungen

Stichworte: Siliciumverbindungen * Silylenoide