Rhodium‐Catalyzed Synthesis of Chiral Monohydrosilanes by Intramolecular C−H Functionalization of Dihydrosilanes

Ma, Wenpeng; Liu, Li‐Chuan; An, Kun; He, Tao; He, Wei

doi:10.1002/ange.202013041

Cited by 18 publications

(1 citation statement)

References 77 publications

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“…[47] The He group adopted the same strategy, as aforementioned above and successfully achieved dihydrosilane steered intramolecular C(sp 2 )À H asymmetric silylation to afford a varity of alkylsubstituted chiral monohydrosilanes with good yield and up to > 99% ee (Scheme 30(a)). [48] According to previous reports, the authors proposed a dehydrogenative pathway to demonstrate intramolecular asymmetric C(sp 2 )À H silylation. The specific reaction mechanism was listed in Scheme 30(b).…”

Section: Dihydrosilane-mediated C(sp 2 )à H Silylationmentioning

confidence: 99%

Recent Progress in Transition Metal‐Catalyzed Hydrosilane‐Mediated C−H Silylation

Kong

2022

Chemistry An Asian Journal

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Organosilicon compounds are widely used in materials science, medicinal chemistry and synthetic chemistry. Recently, significant progress has been achieved in transition metal‐catalyzed dehydrogenative C−H silylation. Particularly, recently developed monohydrosilane and dihydrosilane mediated C−H silylation have emerged as powerful tools in constructing C−Si bonds. Besides, dihydrosilane‐mediated enantioselective asymmetric C−H silylation has successfully enabled the construction of central and helical silicon chirality. In addition, chiral organosilicon compounds have exhibited excellent photoelectric material properties and broad application prospects. Furthermore, organosilicon compounds could under a series of functional group transformations to enrich the diversity of silicon chemistry. This review will present a comprehensive picture of the development of transition metal‐catalyzed hydrosilane‐mediated intramolecular C(sp2)−H and C(sp3)−H silylation organized by their reaction types and mechanisms. In addition, dihydrosilane‐mediated enantioselective asymmetric C−H silylation to construct central and helical silicon chirality will also be highlighted in the review.

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Section: Dihydrosilane-mediated C(sp 2 )à H Silylationmentioning

confidence: 99%

Recent Progress in Transition Metal‐Catalyzed Hydrosilane‐Mediated C−H Silylation

Kong

2022

Chemistry An Asian Journal

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Catalytic Asymmetric Synthesis of Silicon‐Stereogenic Dihydrodibenzosilines: Silicon Central‐to‐Axial Chirality Relay

et al. 2021

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A Rh‐catalyzed asymmetric synthesis of silicon‐stereogenic dihydrodibenzosilines featuring axially chiral 6‐membered bridged biaryls is demonstrated. In the presence of a RhI catalyst with a chiral diphosphine ligand, a wide range of dihydrodibenzosilines containing both silicon‐central and axial chiralities are conveniently constructed in excellent enantioselectivities via dehydrogenative C(sp3)−H silylation. Absolute configuration analysis by single‐crystal X‐ray structures revealed a novel silicon central‐to‐axial chirality relay phenomenon, which we believe will inspire further research in the field of asymmetric catalysis and chiroptical materials.

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Enantioselective Synthesis of Silicon‐Stereogenic Monohydrosilanes by Rhodium‐Catalyzed Intramolecular Hydrosilylation

Huang

Zhu

et al. 2021

Angewandte Chemie

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Enantiopure monohydrosilanes are versatile chiral reagents for alcohol resolution and mechanistic investigation. Herein, we have demonstrated the asymmetric synthesis of monohydrosilanes via an intramolecular hydrosilylation strategy.This protocol is suitable for the synthesis of five-and sixmembered cyclic monohydrosilanes,including aclass of chiral oxasilacycles,w ith excellent diastereo-, regio-, and enantioselectivities.N otably,t he catalyst loading could be reduced to 0.1 mol %which makes this one of the most efficient methods to access chiral monohydrosilanes.M echanistic studies and DFT calculations indicate this Rh-catalyzed intramolecular asymmetric hydrosilylation reaction might proceed via aChalk-Harrod mechanism, and the enantio-determining step was predicted to be oxidative addition of Si À Hb ond.Scheme 1. Asymmetric synthesis of monohydrosilanes.

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Rhodium‐Catalyzed Synthesis of Chiral Monohydrosilanes by Intramolecular C−H Functionalization of Dihydrosilanes

Cited by 18 publications

References 77 publications

Recent Progress in Transition Metal‐Catalyzed Hydrosilane‐Mediated C−H Silylation

Recent Progress in Transition Metal‐Catalyzed Hydrosilane‐Mediated C−H Silylation

Catalytic Asymmetric Synthesis of Silicon‐Stereogenic Dihydrodibenzosilines: Silicon Central‐to‐Axial Chirality Relay

Enantioselective Synthesis of Silicon‐Stereogenic Monohydrosilanes by Rhodium‐Catalyzed Intramolecular Hydrosilylation

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