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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Rhodium hydride enabled enantioselective intermolecular C–H silylation to access acyclic stereogenic Si–H

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Фев. 14, 2022

The tremendous success of stereogenic carbon compounds has never ceased to inspire researchers explore the potentials silicon compounds. Intermolecular C-H silylation thus represents most versatile and straightforward strategy construct C-Si bonds, however, its enantioselective variant been scarcely reported date. Herein we report a protocol that allows for intermolecular bond silylation, leading construction wide array acyclic Si-H under simple mild reaction conditions. Key is (1) substrate design prevents self-reaction prochiral silane (2) employment more reactive rhodium hydride ([Rh]-H) catalyst as opposed commonly used chloride ([Rh]-Cl) catalyst. This work unveils opportunities in converting arenes into value-added

Язык: Английский

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Synthesis of Silicon-Stereogenic Silanols Involving Iridium-Catalyzed Enantioselective C–H Silylation Leading to a New Ligand Scaffold

ACS Catalysis, Год журнала: 2021, Номер 11(17), С. 10748 - 10753

Опубликована: Авг. 13, 2021

Despite a growing focus on the construction of highly enantioenriched silicon-stereogenic organosilicon compounds, enantioselective synthesis silanols through asymmetric catalysis remains considerable challenge. Herein, we realized diarylsilanols via an Ir-catalyzed C–H silylation along with stereospecific substitution or Tamao–Fleming oxidation. This strategy gives rise to class chiral diol catalyst cores (PSiOLs). Transformation PSiOLs led ligand possessing both Si and P-stereocenters, which is capable inducing excellent enantioselectivity in rhodium(I)-catalyzed conjugate 1,4-addition aryl boronic acids cyclohexenone.

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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Cobalt‐Catalyzed Regio‐, Diastereo‐ and Enantioselective Intermolecular Hydrosilylation of 1,3‐Dienes with Prochiral Silanes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(30)

Опубликована: Май 24, 2022

Abstract One of the most straightforward approaches to access chiral silanes is catalytic enantioselective hydrosilylation. Although significant advances have been achieved in construction either a carbon‐stereogenic center or silicon‐stereogenic through hydrosilylation, simultaneous establishment carbon‐ and an acyclic molecule single intermolecular hydrosilylation remained undeveloped. Herein, unprecedented cobalt‐catalyzed regio‐, diastereo‐ 1,3‐dienes presented, enabling transformation. A wide range bearing were generated high efficiency stereoselectivity. Functionalization enantioenriched delivered variety valuable building blocks that are otherwise difficult access.

Язык: Английский

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Enantioselective Synthesis of Spirosilabicyclohexenes by Asymmetric Dual Ring Expansion of Spirosilabicyclobutane with Alkynes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(48)

Опубликована: Окт. 7, 2022

Silaspiranes have attracted particular attention due to their chiral spiro-silicon center, which serves as an ideal carbon isostere and can endow spiro-analogs with distinct properties. Distinct from previously reported cyclization or cycloaddition strategies form 5/5-silaspiranes, we report herein the asymmetric dual ring expansion of spirosilabicyclobutanes alkynes synthesize axially spirosilabicyclohexenes bearing a novel 6/6-silaspirane framework. DFT (density functional theory) calculations provide deep insight into origin high enantioselectivity controlled by sterically demanding binaphthyl phosphoramidite ligand. Preliminary studies chiroptical properties indicate that one spirosilabicyclohexene analogs exhibit fluorescence emission, Cotton effects CPL (circularly polarized luminescence) activity.

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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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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