Organosilicon Synthesis for Construction of Organosilicon Clusters

Kyushin, Soichiro

doi:10.1016/b978-0-12-803530-6.00037-8

Cited by 5 publications

(2 citation statements)

References 51 publications

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“…Silicon-containing compounds are of paramount importance in organic synthesis, polymer science, and biological research. − Historically, silicon atoms were incorporated mainly via nucleophilic substitution of halosilanes , or hydrosilylation with hydrosilanes. − Over the past decades, catalytic direct silylation of C–H bonds has emerged as an attractive strategy that met with numerous progresses. − This new strategy not only embraces the widely conceived advantages of C–H functionalization − (C moiety) but also provides many more choices on silylation reagents (Si moiety). Such combinations of versatile C and Si moieties have greatly enhanced the complexity and diversity of silicon-containing compounds.…”

Section: Introductionmentioning

confidence: 99%

“…Silicon-containing compounds are of paramount importance in organic synthesis, polymer science, and biological research. 1−8 Historically, silicon atoms were incorporated mainly via nucleophilic substitution of halosilanes 9,10 or hydrosilylation with hydrosilanes. 11−17 Over the past decades, catalytic direct silylation of C−H bonds has emerged as an attractive strategy that met with numerous progresses.…”

Section: ■ Introductionmentioning

confidence: 99%

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A Combined Computational and Experimental Study of Rh-Catalyzed C–H Silylation with Silacyclobutanes: Insights Leading to a More Efficient Catalyst System

Zhang

Wang

et al. 2021

J. Am. Chem. Soc.

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The study of new C−H silylation reagents and reactions remains an important topic. We reported that under Rh catalysis, silacyclobutanes (SCBs) for the first time were able to react with C(sp 2 )−H and C(sp 3 )−H bonds, however the underlying reasons for such a new reactivity were not understood. Through this combined computational and experimental study on C−H silylation with SCBs, we not only depict a reaction pathway that fully accounts for the reactivity and all the experimental findings but also streamline a more efficient catalyst that significantly improves the reaction rates and yields. Our key findings include: (1) the active catalytic species is a [Rh]−H as opposed to the previously proposed [Rh]−Cl; (2) the [Rh]−H is generated via a reductive elimination/β-hydride (β-H) elimination sequence, as opposed to previously proposed endocyclic β-H elimination; (3) the regio-and enantio-determining steps are identified; (4) and of the same importance, the discretely synthesized [Rh]−H is shown to be a more efficient catalyst. This work suggests that the [Rh]−H/diphosphine system should find further applications in C−H silylations involving SCBs.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

A Combined Computational and Experimental Study of Rh-Catalyzed C–H Silylation with Silacyclobutanes: Insights Leading to a More Efficient Catalyst System

Zhang

Wang

et al. 2021

J. Am. Chem. Soc.

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Lewis Base Catalyzed Selective Chlorination of Monosilanes

Sturm

Schweizer

Meyer

et al. 2018

Chemistry A European J

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A preparatively facile, highly selective synthesis of bifunctional monosilanes R SiHCl, RSiHCl and RSiH Cl is reported. By chlorination of R SiH and RSiH with concentrated HCl/ether solutions, the stepwise introduction of Si-Cl bonds is readily controlled by temperature and reaction time for a broad range of substrates. In a combined experimental and computational study, we establish a new mode of Si-H bond activation assisted by Lewis bases such as ethers, amines, phosphines, and chloride ions. Elucidation of the underlying reaction mechanisms shows that alcohol assistance through hydrogen-bond networks is equally efficient and selective. Remarkably, formation of alkoxysilanes or siloxanes is not observed under moderate reaction conditions.

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