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 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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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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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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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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Copper-catalyzed intermolecular Regio- and Enantioselective Hydrosilylation of Alkenes with Prochiral Silanes

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 3, 2025

This study presents a copper-catalyzed, substrate-controlled regio- and enantioselective intermolecular hydrosilylation method capable of accommodating broad scope alkenes prochiral silanes. The approach offers an efficient versatile pathway to generate enantioenriched linear branched alkyl-substituted Si-stereogenic Key features this reaction include mild conditions, simple catalytic systems, compatibility with diverse substrates, high yields enantioselectivities. While methods create chiral carbon centers stereochemically defined silicon have been developed, the ability both simultaneously would be value. Here authors present substratecontrolled

Язык: Английский

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Enantioselective Hydroxylation of Dihydrosilanes to Si‐Chiral Silanols Catalyzed by In Situ Generated Copper(II) Species

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(32)

Опубликована: Июнь 2, 2022

Catalytic enantioselective hydroxylation of prochiral dihydrosilanes with water is expected to be a highly efficient way access Si-chiral silanols, yet has remained unknown up date. Herein, we describe strategy for realizing this reaction: using an alkyl bromide as single-electron transfer (SET) oxidant invoking CuII species and chiral multidentate anionic N,N,P-ligands effective enantiocontrol. The reaction readily provides broad range silanols high enantioselectivity excellent functional group compatibility. In addition, manifest the synthetic potential by establishing two schemes transforming obtained products into compounds structural diversity. Our preliminary mechanistic studies support mechanism involving SET recruiting active catalyst its subsequent σ-metathesis dihydrosilanes.

Язык: Английский

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Highly Regioselective Cobalt‐Catalyzed Hydroboration of Internal Alkynes

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

Опубликована: Июль 13, 2022

Herein, we report the development of new Co complexes that have cyclopropane-based diphosphine ligands and can catalyze highly chemo-, regio-, stereoselective hydroboration reactions unsymmetrical internal alkynes. These exhibited unusual regioselectivity: specifically, aryl alkyl alkynes showed excellent cis-β-addition selectivity, dialkyl gave cis-α-addition selectivity. Highly regioselective cannot be achieved by other known methods. The described herein are synthetically useful, particularly for synthesis trisubstituted alkenylborates alkenes. Mechanistic studies indicate a CoI -H species is plausible active catalyst rigid structure cyclopropane skeleton crowded reaction pocket were responsible unprecedented regioselectivity.

Язык: Английский

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Atroposelective Synthesis of Axially Chiral Styrenes by Platinum‐ Catalyzed Stereoselective Hydrosilylation of Internal Alkynes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 25, 2023

Abstract Hydrofunctionalization of alkynes is one the most efficient ways to access axially chiral styrenes with open‐chained olefins. While great advances have been achieved for 1‐alkynylnaphthalen‐2‐ols and analogues, atroposelective hydrofunctionalization unactivated internal lags. Herein we reported a platinum‐catalyzed hydrosilylation first time. With monodentate TADDOL‐derived phosphonite L1 used as ligand, various were in excellent enantioselectivities high E ‐selectivities. Control experiments showed that N H‐arylamide groups significant effects on both yields could act directing groups. The potential utilities products shown by transformations amide motifs products.

Язык: Английский

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