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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Chiral PSiSi‐Ligand Enabled Iridium‐Catalyzed Atroposelective Intermolecular C−H Silylation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)

Опубликована: Июль 18, 2023

Catalytic enantioselective intermolecular C-H silylation offers an efficient approach for the rapid construction of chiral organosilicon compounds, but remains a significant challenge. Herein, new type silyl ligand is developed, which enables first iridium-catalyzed atroposelective reaction 2-arylisoquinolines. This protocol features mild conditions, high atom economy, and remarkable yield with excellent stereoselectivity (up to 99 % yield, ee), delivering enantioenriched axially silane platform molecules facile convertibility. Key success this unprecedented transformation relies on novel PSiSi-ligand, facilitates process perfect chem-, regio- stereo-control via multi-coordinated iridium complex.

Язык: Английский

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Organocatalytic enantioselective construction of Si-stereocenters: recent advances and perspectives

Chemical Society Reviews, Год журнала: 2024, Номер 53(17), С. 8546 - 8562

Опубликована: Янв. 1, 2024

Silicon-stereogenic chiral organosilanes have found increasing applications in synthetic chemistry, medicinal and materials science. In this context, various asymmetric catalytic methods been established for the diverse synthesis of silicon-stereogenic silanes. particular, organocatalysis is emerging as an important complementary tool enantioselective construction silicon-stereocenters, along with rapid development chiral-metal catalyzed protocols. Its advent provides a powerful platform to achieve functionalized structural diversity, should lead great organosilicon chemistry. Tutorial Review, we highlight these latest achievements from two aspects: desymmetrizations prochiral tetraorganosilanes dynamic kinetic transformations racemic by employing five organocatalytic activation modes. The advantages, limitations value each protocol, well opportunities still open further exploration, are also discussed.

Язык: Английский

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Copper‐Catalyzed Asymmetric Synthesis of Silicon‐Stereogenic Benzoxasiloles

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(7)

Опубликована: Янв. 5, 2024

Abstract A Cu‐catalyzed asymmetric synthesis of silicon‐stereogenic benzoxasiloles has been realized via intramolecular Si−O coupling [2‐(hydroxymethyl)phenyl]silanes. Cu(I)/difluorphos is found to be an efficient catalytic system for enantioselective Si−C bond cleavage and formation. In addition, kinetic resolution racemic substituted [2‐(hydroxymethyl)phenyl]silanes using Cu(I)/ PyrOx (pyridine‐oxazoline ligands) as the developed afford carbon‐ benzoxasiloles. Ring‐opening reactions chiral with organolithiums Grignard reagents yield various enantioenriched functionalized tetraorganosilanes.

Язык: Английский

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X-type silyl ligands for transition-metal catalysis

Chemical Society Reviews, Год журнала: 2024, Номер 53(9), С. 4648 - 4673

Опубликована: Янв. 1, 2024

This review summarizes the developments of X-type silyl ligands for transition-metal catalysis, elucidating unique features σ-donating ability and trans -influence silyl–metal catalysts.

Язык: Английский

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The role of silicon in drug discovery: a review

RSC Medicinal Chemistry, Год журнала: 2024, Номер 15(10), С. 3286 - 3344

Опубликована: Янв. 1, 2024

This review aims to highlight the role of silicon in drug discovery.

Язык: Английский

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Lewis Base-Catalyzed Dynamic Kinetic Asymmetric Transformation of Racemic Chlorosilanes en Route to Si-Stereogenic Silylethers

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(33), С. 23092 - 23102

Опубликована: Авг. 7, 2024

Enantiopure Si-stereogenic organosilanes are highly valued in the fields of organic synthesis, development advanced materials, and drug discovery. However, they not naturally occurring, their synthesis has been largely confined to resolution racemic silanes or desymmetrization symmetric silanes. In contrast, dynamic kinetic asymmetric transformation (DYKAT) offers a mechanistically distinct approach would broaden accessibility an enantioconvergent manner. this study, we report Lewis base-catalyzed DYKAT chlorosilanes. The chiral isothiourea catalyst, (S)-benzotetramisole, facilitates silyletherification with phenols, yielding (R)-silylethers good yields high enantioselectivity (27 examples, up 86% yield, 98:2 er). Kinetic analysis, control experiments, DFT calculations suggest that two-catalyst-bound pentacoordinate silicate is responsible for Si-configurational epimerization ion-paired tetracoordinated silicon intermediates.

Язык: Английский

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