Hydrosilylation of Carbon–Carbon Multiple Bonds—Application in Synthesis and Materials Science

Marciniec, Bogdan; Maciejewski, Hieronim; Pawluć, Piotr

doi:10.1016/b978-0-12-814213-4.00005-8

Cited by 15 publications

(17 citation statements)

References 204 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%

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%

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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“…Moreover, benefiting from the unique atomic properties of silicon, silicon analogues play important roles in drug discovery (Figure , b) . Alkene hydrosilylation is one major approach widely used in industry to provide commodity silicones after the Direct Process . However, application of this atom-economic strategy in fine chemical synthesis, such as the above-mentioned areas, is much less common (Scheme , a).…”

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confidence: 99%

Iridium-Catalyzed Hydrosilylation of Unactivated Alkenes: Scope and Application to Late-Stage Functionalization

et al. 2018

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“…Slightly better results, although still unsatisfactory, were observed for molecular catalysts (Pt 2 (dvs) 3 and H 2 PtCl 6 ), which are highly active with the addition of Si–H to the C≡C bonds ( Table 1 , entries 4–6). 48 The highest activity toward the B–B bond addition to 2a was shown by relatively air-stable [Pt(PPh 3 ) 4 ], which led to a monoadduct ( 3a ) with excellent yield ( Table 1 , entry 8). The addition of the phosphine ligand Xphos had a negative influence on the conversion and reaction selectivity ( Table 1 , entry 7).…”

Section: Resultsmentioning

confidence: 99%

“…The heterogeneous catalysts (PtO 2 and Pt/C) did not show activity under the applied reaction conditions (Table , entries 1–3). Slightly better results, although still unsatisfactory, were observed for molecular catalysts (Pt 2 (dvs) 3 and H 2 PtCl 6 ), which are highly active with the addition of Si–H to the CC bonds (Table , entries 4–6) . The highest activity toward the B–B bond addition to 2a was shown by relatively air-stable [Pt(PPh 3 ) 4 ], which led to a monoadduct ( 3a ) with excellent yield (Table , entry 8).…”

Section: Resultsmentioning

confidence: 99%

[Pt(PPh₃)₄]-Catalyzed Selective Diboration of Symmetrical and Unsymmetrical 1,3-Diynes

et al. 2022

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A straightforward, efficient, and selective method for the preparation of novel boryl-functionalized enynes or dienes via [Pt(PPh 3 ) 4 ]-catalyzed diboration of a broad spectrum of symmetrical and unsymmetrical 1,3-diynes was developed. The catalytic cycle of diboration was proposed on the basis of low-temperature 31 P NMR studies. An alternative isolation method via product condensation on a cold finger was developed, which, in contrast to previous literature reports, eliminates the need for the additional transformation of rapidly decomposing enynyl pinacol boronates to more stable silica-based column chromatography derivatives during the separation step. To prove the efficiency of this simple catalytic protocol, bisboryl-functionalized enynes were synthesized in a gram scale and tested as useful building blocks in advanced organic transformations, such as hydrosilylation and Suzuki and sila-Sonogashira couplings. The presence of silyl, boryl, as well as other functions like halogen or alkoxy in their structures builds a new class of multifunctionalized enynes that might be modified in various chemical reactions.

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Hydrosilylation of Carbon–Carbon Multiple Bonds—Application in Synthesis and Materials Science

Cited by 15 publications

References 204 publications

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

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

Iridium-Catalyzed Hydrosilylation of Unactivated Alkenes: Scope and Application to Late-Stage Functionalization

[Pt(PPh₃)₄]-Catalyzed Selective Diboration of Symmetrical and Unsymmetrical 1,3-Diynes

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Hydrosilylation of Carbon–Carbon Multiple Bonds—Application in Synthesis and Materials Science

Cited by 15 publications

References 204 publications

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

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

Iridium-Catalyzed Hydrosilylation of Unactivated Alkenes: Scope and Application to Late-Stage Functionalization

[Pt(PPh3)4]-Catalyzed Selective Diboration of Symmetrical and Unsymmetrical 1,3-Diynes

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Product

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[Pt(PPh₃)₄]-Catalyzed Selective Diboration of Symmetrical and Unsymmetrical 1,3-Diynes