Synthesis of Atropisomers by Transition-Metal-Catalyzed Asymmetric C–H Functionalization Reactions

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(35), P. 14025 - 14040

Published: Aug. 25, 2021

Transition-metal-catalyzed enantioselective C-H functionalization has become a powerful strategy for the formation of C-C or C-X bonds, enabling highly asymmetric synthesis wide range enantioenriched compounds. Atropisomers are widely found in natural products and pharmaceutically relevant molecules, have also applications as privileged frameworks chiral ligands catalysts. Thus, research into routes atropisomers garnered great interest recent years. In this regard, transition-metal-catalyzed emerged an atom-economic efficient toward their synthesis. Perspective, approaches by reactions summarized. The main focus here is on catalysis via Pd, Rh, Ir complexes, which been most frequently utilized catalysts among reported reactions. Finally, we discuss limitations available protocols give outlook possible future avenues research.

Language: Английский

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Recent Progress toward the Construction of Axially Chiral Molecules Catalyzed by an N-heterocyclic Carbene

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(20), P. 12520 - 12531

Published: Sept. 28, 2021

Axial chirality widely exists in natural products, pharmaceutical compounds, and other functional molecules; these axially chiral compounds also find wide utility as catalysts or ligands organic synthetic chemistry. Nevertheless, whereas significant progress has been made toward the synthesis of enantioenriched molecules over past two decades, strategies involving organocatalysis have only started to emerge recently. N-heterocyclic carbene (NHC) organocatalysts recognized be powerful tools for rapid construction complex molecular architectures. However, previous works mainly focused on assembly point recently it realized that asymmetric axial could achieved by using NHCs organocatalysts. This Perspective highlights developments advances scaffolds catalyzed NHCs. The aim this is provide an overview area serve a stepping stone future investigations.

Language: Английский

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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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Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Nov. 2, 2023

With the rapid development of asymmetric catalysis, demand for enantioselective synthesis complex and diverse molecules with different chiral elements is increasing. Owing to unique features atropisomerism, catalytic atropisomers has attracted a considerable interest from chemical science community. In particular, introducing additional elements, such as carbon centered chirality, heteroatomic planar helical into provides an opportunity incorporate new properties axially compounds, thus expanding potential applications atropisomers. Thus, it important perform transformations synthesize bearing multiple elements. spite challenges in transformations, recent years, chemists have devised powerful strategies under organocatalysis or metal synthesizing wide range enantioenriched Therefore, become emerging field. This review summarizes progress this field indicates challenges, thereby promoting horizon.

Language: Английский

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Catalytic Asymmetric Construction of Axially and Centrally Chiral Heterobiaryls by Minisci Reaction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(13), P. 6040 - 6049

Published: March 24, 2022

Axially chiral biaryls and heterobiaryls constitute the most represented subclass of atropisomers with prevalence in natural products, bioactive compounds, privileged ligand/catalysts, optically pure materials. Despite many ionic protocols for their construction, radical-based variants represent another highly desirable intriguing strategy but are far less developed. Moreover, efficient synthesis axially heterobiaryl molecules, especially ones having multiple heteroatoms other types elements, through radical routes remains extremely limited. We herein disclose first catalytic asymmetric, metal-free construction centrally by Minisci reaction 5-arylpyrimidines α-amino acid-derived redox-active esters. This is enabled use 4CzIPN as an organic photoredox catalyst conjunction a phosphoric acid catalyst. The achieved variety interesting featuring union α-branched amine generally excellent regio-, diastereo-, enantioselectivity (up to 82% yield; >19:1 dr; >99% ee). finding also builds up new platform development desymmetrization methods via radical-involved atroposelective functionalization at heteroarene prochiral heterobiaryls.

Language: Английский

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Nickel(0)‐Catalyzed Asymmetric Ring Expansion Toward Enantioenriched Silicon‐Stereogenic Benzosiloles

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(49), P. 25723 - 25728

Published: Sept. 30, 2021

The development of a straightforward strategy to obtain enantioenriched silicon-stereogenic benzosiloles remains challenging yet appealing synthesis venture due their potential future application in chiral electronic and optoelectronic devices. In this context, all the existing methods rely on Rh-catalyzed systems are somewhat limited scope. Herein, we disclose first Ni0 -catalyzed ring expansion process that enables preparation possessing tetraorganosilicon stereocenters excellent yields enantioselectivities. presented catalysis is further applied asymmetric bis-silicon-bridged π-extended systems. Preliminary studies reveal such compounds exhibit fluorescence emission, Cotton effects circularly polarized luminescence (CPL) activity.

Language: Английский

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Catalytic Enantioselective Construction of Chiroptical Boron-Stereogenic Compounds

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(39), P. 16302 - 16310

Published: Sept. 27, 2021

The construction of main group heteroatom-stereogenic compounds is great importance due to their intriguing chemical, physical, biological, and stereoelectronic properties. Despite that organoboron are widely used in organic chemistry, the creation a tetrahedral boron-stereogenic center one enantiomeric form remains highly challenging. Given labile nature ligands attached tetracoordinate boron atom, only handful enantioenriched have been reported via resolution or chiral substrate-induced diastereoselective approach. To date catalytic asymmetric synthesis has remained unknown. Here, we demonstrate first enantioselective an copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. This CuAAC reaction not gives access wide range novel functionalized heterocycles high yields with good excellent enantioselectivities but also produces optically active terminal alkyne triazole moieties various potential application prospects. Further transformation delivers several complex heterocyclic entities bearing centers without loss enantiopurity. Moreover, X-ray structure, barrier racemization, HOMO/LUMO gap selected investigated. Notably, these N,N π-conjugated exhibit bright fluorescence. optical properties, including circular dichroism, quantum yield, polarized luminescence spectroscopies, examined. These features expand chemical space chiroptical boron-based dye platform, which could applications optoelectronic materials.

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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Construction of Si‐Stereogenic Silanes through C−H Activation Approach

European Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 2021(44), P. 6006 - 6014

Published: Sept. 21, 2021

Abstract The asymmetric synthesis of Si‐stereogenic silanes has attracted great attention due to the increasing values Si‐containing functional molecules in synthetic chemistry, medicinal and material chemistry. Merging organosilicon chemistry with transition‐metal‐catalyzed C−H approach led rich sets new reactions holding values. This Minireview aims summarize advances construction through activation approach.

Language: Английский

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