Enantioselective Intermolecular C−H Silylation of Heteroarenes for the Synthesis of Acyclic Si‐Stereogenic Silanes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(21)

Опубликована: Март 8, 2022

Intermolecular C-H silylation for the synthesis of acyclic silanes bearing a silicon-stereogenic center in one enantiomeric form remains unknown to date. Herein, we report first enantioselective intermolecular heteroarenes heteroarylsilanes. This process undergoes rhodium-catalyzed direct dehydrogenative Si-H/C-H cross-coupling, giving access variety heteroarylated monohydrosilanes, including bis-Si-stereogenic silanes, decent yields with excellent chemo-, regio-, and stereo-control, which significantly enlarge chemical space optically active monohydrosilanes.

Язык: Английский

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Transition-metal-catalyzed enantioselective C−H silylation

Chem Catalysis, Год журнала: 2022, Номер 2(11), С. 2898 - 2928

Опубликована: Авг. 15, 2022

Язык: Английский

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Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Май 20, 2022

Abstract Optically active organosilanes have been demonstrated to be versatile chiral reagents in synthetic chemistry since the early seminal contributions by Sommer and Corriu. Among these silicon‐containing architectures, monohydrosilanes, which bear a Si−H bond, hold unique position because of their facile transformations through stereospecific Si–carbon or Si–heteroatom bond‐formation reactions. In addition, those compounds also leveraged as for alcohol resolution, auxiliaries, mechanistic probes, well potential optoelectronic materials. This Minireview comprehensively summarizes synthesis applications silicon‐stereogenic particularly advances transition‐metal‐catalyzed asymmetric this class functional molecules.

Язык: Английский

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Synthesis of Si‐Stereogenic Silanols by Catalytic Asymmetric Hydrolytic Oxidation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(31)

Опубликована: Май 26, 2022

Despite growing progress in the construction of chiral organosilicon compounds, catalytic asymmetric synthesis silicon-stereogenic silanols is less explored and remains a considerable challenge. Herein, we report first enantioselective by hydrolytic oxidation dihydrosilanes. This practical procedure features ambient reaction conditions, high atom economy, good functional-group compatibility, H2 as only by-product, produces wide range valuable bis-silanols decent yields with excellent chemo- stereoselectivity.

Язык: Английский

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Copper-Catalyzed Desymmetrization of Prochiral Silanediols to Silicon-Stereogenic Silanols

ACS Catalysis, Год журнала: 2022, Номер 12(14), С. 8476 - 8483

Опубликована: Июль 1, 2022

Despite the growing demand for enantioenriched silicon-stereogenic silanols in materials science, medicinal chemistry, and modern synthetic catalytic asymmetric synthesis of which remains a considerable challenge compared with their carbinol analogues. Herein, copper-catalyzed desymmetrization silanediols various functionalized chiral is demonstrated. The reaction features high atom economy, decent yield excellent stereoselectivity, H2 as sole byproduct. Key to success discrimination gem-diol groups silanediol relies on an enantioselective σ-bond metathesis process. Further straightforward elaboration delivers several interesting silane scaffolds without loss enantiopurities.

Язык: Английский

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Rhodium‐Catalyzed Dynamic Kinetic Asymmetric Hydrosilylation to Access Silicon‐Stereogenic Center

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(51)

Опубликована: Ноя. 4, 2022

Abstract Strategies on the construction of enantiomerically pure silicon‐stereogenic silanes generally relies desymmetrization prochiral and symmetric substrates. However, dynamic kinetic asymmetric transformations organosilicon compounds have remained underdeveloped unforeseen owing to a lack an effective method for deracemization static silicon stereocenters. Here we report first Rh‐catalyzed intramolecular hydrosilylation (DyKAH) with “silicon‐centered” racemic hydrosilanes that enables facile preparation benzosiloles in good yields excellent enantioselectivities. The special rhodium catalyst controlled by non‐diastereopure‐type mixed phosphine‐phosphoramidite ligand axial chirality multiple stereocenters can induce enantioselectivity efficiently this novel DyKAH reaction. Density functional theory (DFT) calculations suggest amide moiety chiral plays important role facilitating S N 2 substitution chloride ion realize inversion center.

Язык: Английский

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Catalytic asymmetric silicon-carbon bond-forming transformations based on Si-H functionalization

Science China Chemistry, Год журнала: 2023, Номер 66(6), С. 1654 - 1687

Опубликована: Май 4, 2023

Язык: Английский

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Highly Enantioselective Construction of Multifunctional Silicon‐Stereogenic Silacycles by Asymmetric Enamine Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(9)

Опубликована: Янв. 10, 2023

We report the first highly enantioselective construction of silicon-stereocenters by asymmetric enamine catalysis. An unprecedented desymmetric intramolecular aldolization prochiral siladials was thus developed for facile access multifunctional silicon-stereogenic silacycles in high to excellent enantioselectivity. With an enal moiety, these adducts could be readily elaborated diverse synthesis compounds, and late-stage modification.

Язык: Английский

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Chiral Silanols: Strategies and Tactics for Their Synthesis

Chemistry - A European Journal, Год журнала: 2023, Номер 29(19)

Опубликована: Янв. 9, 2023

Silanols are valuable and important compounds, which have found widespread applications in the field of materials science, synthetic chemistry, medicinal chemistry. Although a handful approaches been developed for synthesis various silanols, access to enantioenriched silicon-stereogenic silanols remains underdeveloped. This Concept article intends summarize highlight recent advances construction endeavors encourage further research this area.

Язык: Английский

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Catalytic asymmetric synthesis of silicon-stereogenic organosilanes

Chem, Год журнала: 2023, Номер 9(12), С. 3461 - 3514

Опубликована: Окт. 19, 2023

Язык: Английский

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