Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Language: Английский

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Enantioselective C–H Functionalization toward Silicon-Stereogenic Silanes

Synthesis, Journal Year: 2022, Volume and Issue: 54(08), P. 1939 - 1950

Published: Jan. 3, 2022

Abstract In recent years, transition-metal-catalyzed enantioselective C–H bond functionalization has emerged as a powerful and attractive synthetic approach to access silicon-stereogenic centers, which provides impetus for the innovation of chiral organosilicon chemistry. This short review summarizes advances in construction silanes via functionalization. We endeavor highlight great potential this methodology hope that will shed light on new perspectives inspire further research emerging area. 1 Introduction 2 Enantioselective Functionalization Induced by Oxidative Addition­ an Aryl-OTf Bond 3 Silacyclobutane 4 Directing-Group-Assisted 5 Dehydrogenative C–H/Si–H Coupling 5.1 C(sp2)–H Silylation 5.2 C(sp3)–H 6 Summary Outlook

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(21)

Published: March 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.

Language: Английский

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Transition-metal-catalyzed enantioselective C−H silylation

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(11), P. 2898 - 2928

Published: Aug. 15, 2022

Language: Английский

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Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: May 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.

Language: Английский

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Synthesis of Si‐Stereogenic Silanols by Catalytic Asymmetric Hydrolytic Oxidation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 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.

Language: Английский

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

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(14), P. 8476 - 8483

Published: July 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.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(51)

Published: Nov. 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.

Language: Английский

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

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(6), P. 1654 - 1687

Published: May 4, 2023

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(9)

Published: Jan. 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.

Language: Английский

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