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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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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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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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 Dehydrogenative Si–H/N–H Coupling: Synthesis of Silicon-Stereogenic Silazanes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(21), С. 11727 - 11734

Опубликована: Май 19, 2023

Despite growing progress in the construction of silazanes, catalytic asymmetric synthesis silicon-stereogenic silazanes is significantly less explored and remains a considerable challenge. Herein, we report highly enantioselective via dehydrogenative coupling dihydrosilanes with anilines. The reaction readily produces wide range chiral bis-silazanes excellent yields stereoselectivities (up to 99% ee). Further utility this process demonstrated by polycarbosilazanes featuring configurational main chain chirality. In addition, straightforward transformation enantioenriched delivers various silane compounds stereospecific fashion, illustrating their potential utilities as synthons for novel silicon-containing functional molecules.

Язык: Английский

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Axial chirality reversal and enantioselective access to Si-stereogenic silylallene

Chem, Год журнала: 2023, Номер 9(10), С. 2956 - 2970

Опубликована: Июль 18, 2023

Язык: Английский

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Organocatalytic DYKAT of Si-Stereogenic Silanes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(9), С. 4994 - 5000

Опубликована: Фев. 24, 2023

Chiral organosilanes do not exist in nature and are therefore absent from the "chiral pool". As a consequence, synthetic approaches toward enantiopure silanes, stereogenic at silicon, rather limited. While catalytic asymmetric desymmetrization reactions of symmetric organosilicon compounds have been developed, utilization racemic silanes dynamic kinetic transformation (DYKAT) or resolution (DKR) would significantly expand breadth accessible Si-stereogenic compounds. We now report DYKAT allyl enabled by strong confined imidodiphosphorimidate (IDPi) catalysts, providing access to silyl ethers. The products this reaction easily converted into useful monohydrosilanes. propose spectroscopically experimentally supported mechanism involving epimerization catalyst-bound intermediate.

Язык: Английский

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Catalytic Kinetic Resolution of Monohydrosilanes via Rhodium‐Catalyzed Enantioselective Intramolecular Hydrosilylation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(25)

Опубликована: Апрель 12, 2024

The catalytic access of silicon-stereogenic organosilanes remains a big challenge, and largely depends on the desymmetrization symmetric precursors with two identical substitutes attached to silicon atom. Here we report construction via kinetic resolution racemic monohydrosilanes good excellent selectivity factors. Both Si-stereogenic dihydrobenzosiloles could be efficiently accessed in one single operation Rh-catalyzed enantioselective intramolecular hydrosilylation, employing (R,R)-Et-DuPhos as optimal ligand. This protocol features mild conditions, low catalyst loading (0.1 mol % [Rh(cod)Cl]

Язык: Английский

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