3724-36-5Relevant articles and documents
Custom Hydrosilane Synthesis Based on Monosilane
Yuan, Weiming,Smirnov, Polina,Oestreich, Martin
, p. 1443 - 1450 (2018/04/20)
The omnipresence of silicon compounds with carbon substituents in synthetic chemistry hides the fact that, except for certain substitution patterns at the silicon atom, their preparation is often far from trivial. The challenge is rooted in the lack of control over nucleophilic substitution with carbon nucleophiles at silicon atoms with three or four leaving groups. For example, SiCl4 usually converts into intractable mixtures of chlorosilanes, typically requiring several distillation cycles to reach high purity. Accordingly, there is no universal approach to silanes with heteroleptic substitution. Here, using a bench-stable SiH4 surrogate, we introduce a general strategy for the on-demand synthesis of silicon compounds decorated with different aryl and alkyl substituents. Reliable protocols are the basis of the selective and programmable synthesis of dihydro- and monohydrosilanes; aryl-substituted trihydrosilanes are also accessible in a straightforward fashion. These otherwise difficult-to-access hydrosilanes are only three or fewer easy synthetic operations away from the SiH4 surrogate. Synthesizing silicon compounds with different carbon substituents from inorganic silicon precursors, i.e., basic silicon chemicals with hydrogen, halogen, or alkoxy substitution, is an intricate and often insoluble task. It is generally difficult to chemoselectively address one of these groups in chemical reactions, particularly when two or more of those are identical. Complicated separation and purification procedures are the result. The challenge of making these silicon compounds containing silicon–carbon bonds, typically hydro- and chlorosilanes, is accentuated considering their high demand in academia and industry. The present approach is a step forward in solving those limitations. It hinges on the stepwise decoration of the silicon atom of a liquid monosilane surrogate. Further development of this strategy and adjusting it to industrial needs could pave the way to easy access of an even more diverse manifold of silicon compounds for synthetic chemistry and material science. Oestreich and colleagues present an approach to the chemoselective stepwise preparation of hydrosilanes with the general formula R4–nSiHn where n = 1–3 and R can be different aryl and alkyl groups. The starting point is a bench-stable SiH4 surrogate with two Si–H bonds masked as cyclohexa-2,5-dien-1-yl substituents. A sequence of palladium-catalyzed Si–H arylation and B(C6F5)3-promoted deprotection and transfer hydrosilylation enables the programmable synthesis of hydrosilanes, even with three different substituents at the silicon atom.
CARBON-SILICON BOND CLEAVAGE OF ORGANOTRIALKOXYSILANES AND ORGANOSILATRANES WITH m-CHLOROPERBENZOIC ACID AND N-BROMOSUCCINIMIDE. NEW ROUTE TO PHENOLS, PRIMARY ALCOHOLS AND BROMIDES
Hosomi, Akira,Iijima, Susumu,Sakurai, Hideki
, p. 243 - 246 (2007/10/02)
Alkyl- and aryltriethoxysilanes undergo oxidative carbon-silicon bond cleavage smoothly with m-chloroperbenzoic acid (MCPBA) to afford the corresponding alcohols.Silatranes similarly gave alcohols and bromides with MCPBA and N-bromosuccinimide, respectively.
