Recent Advances in Catalytic Asymmetric Construction of Atropisomers

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(8), P. 4805 - 4902

Published: March 27, 2021

Atropisomerism is a stereochemical behavior portrayed by three-dimensional molecules that bear rotationally restricted σ bond. Akin to the well-represented point-chiral molecules, atropisomerically chiral compounds are finding increasing utilities in many disciplines where molecular asymmetry influential. This provides steady demand on atroposelective synthesis, numerous synthetic pursuits have been rewarded with conceptually novel and streamlined methods while expanding structural diversity of atropisomers. review summarizes key achievements stereoselective preparation biaryl, heterobiaryl, nonbiaryl atropisomers documented between 2015 2020. Emphasis placed strategies for each class, examples cited illustrate potential applications accessed atropochiral targets.

Language: Английский

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Recent advances in the synthesis of axially chiral biarylsviatransition metal-catalysed asymmetric C–H functionalization

Chemical Communications, Journal Year: 2019, Volume and Issue: 55(59), P. 8514 - 8523

Published: Jan. 1, 2019

Recent advances in the synthesis of axially chiral biarylsviatransition metal-catalysed asymmetric C–H functionalization are reported.

Language: Английский

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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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Organocatalytic Atroposelective Synthesis of Indole Derivatives Bearing Axial Chirality: Strategies and Applications

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(18), P. 2562 - 2580

Published: Sept. 2, 2022

Catalytic atroposelective syntheses of axially chiral compounds have stimulated extensive interest in multiple communities, such as synthetic chemistry, biochemistry, and materials science, because the intriguing characteristics atropisomerism. In particular, atropisomeric indole derivatives, which contain a kind five-membered heterocyclic framework, are widely distributed number natural alkaloids, biologically relevant compounds, ligands, organocatalysts. Hence, catalytic synthesis derivatives bearing axial chirality is considerable importance has become an emerging focus research. However, there substantial challenges associated with including remote ortho-substituents around axis, lower barrier for rotation, weaker configurational stability than that six-membered biaryls. Therefore, development effective strategies toward urgent task.In order to tackle these accomplish task, our group devised unique strategy designing indole-derived platform molecules developing organocatalytic enantioselective transformations synthesize derivatives; asymmetric organocatalysis tremendous advantages was research area recognized by Nobel Prize Chemistry 2021. This Account summarizes endeavors chirality. brief, we developed series molecules, indolylmethanols, (hetero)aryl indoles, oxindole-based styrenes, N-aminoindoles, indole-based homophthalic anhydrides, introducing different functional groups onto ring achieve new reactivity modulate reactive site ring. As result, possess versatile capable undergoing variety preparing structurally diversified chirality.We used plenty chirality, alkene-indoles, N-pyrrolylindoles, isochromenone-indoles. addition, gave thorough detailed understanding designed reaction investigating pathway activation mode. More importantly, studied biological activity some products performed catalyst design on basis moieties, helpful disclosing more applications chirality.In future, will indubitably remain frontier topic catalysis chemistry despite challenging issues, instance, novel unconventional into powerful catalysts or discovery potent drug candidates. We hope efforts summarized this encourage chemists worldwide devise innovative solving issues field, thus promoting its higher level.

Language: Английский

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Catalytic Asymmetric Construction of Axially Chiral Indole‐Based Frameworks: An Emerging Area

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(68), P. 15779 - 15792

Published: May 4, 2020

Axially chiral indole-based frameworks have been recognized as a class of important five-membered heterobiaryls and developing catalytic asymmetric approaches for constructing these in an enantioselective manner is highly desirable. In recent years, synthetic chemists paid much attention to this research field, rapid developments occurred. At point, range axially scaffolds constructed via various reactions based on different strategies. Thus, the construction has become emerging area. This minireview summarizes advances field gives some insights into future developments, which will help thrive.

Language: Английский

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A Bulky Chiral N-Heterocyclic Carbene Palladium Catalyst Enables Highly Enantioselective Suzuki–Miyaura Cross-Coupling Reactions for the Synthesis of Biaryl Atropisomers

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(37), P. 14938 - 14945

Published: Aug. 28, 2019

Axially chiral biaryl scaffolds are essential structural units in chemistry. The asymmetric Pd-catalyzed Suzuki–Miyaura cross-coupling reaction has been widely recognized as one of the most practical methods for constructing atropisomers biaryls. However, longstanding challenges remain this field. For example, substrate scope is often narrow and specialized, functional groups heterocycles can lead to reduced reactivity selectivity, bulky ortho-substituents usually needed, reported generally inapplicable tetra-ortho-substituted We have developed an unprecedented highly enantioselective N-heterocyclic carbene (NHC)-Pd catalyzed synthesis atropisomeric These reactions enable efficient coupling aryl halides (Br, Cl) or triflates with various types boron compounds (B(OH)2, Bpin, Bneo, BF3K), tolerate a remarkably broad (>41 examples), employ low loading catalyst (0.2–2 mol %), proceed under mild conditions. protocol provided general access biaryls heterobiaryls excellent enantioselectivities (up 99% ee) no need using ortho-substituted substrates was effective tetra-ortho-substituent Moreover, method successfully applied diastereo- ternaphthalenes. Critical success development application extremely C2-symmetric NHC, (R,R,R,R)-DTB-SIPE, ligand palladium. To best our knowledge, first (>90% example NHC-metal-catalyzed C(sp2)–C(sp2) reaction.

Language: Английский

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Chiral Cyclopentadienyl Ligands: Design, Syntheses, and Applications in Asymmetric Catalysis

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(24), P. 13198 - 13224

Published: July 16, 2020

The creation of new chiral ligands capable providing high stereocontrol in metal-catalyzed reactions is crucial modern organic synthesis. production bioactive molecules as single enantiomers increasingly required, and asymmetric catalysis with metal complexes constitutes one the most efficient synthetic strategies to access optically active compounds. Herein we offer a historical overview on development derivatives ubiquitous cyclopentadienyl ligand (CpX ), detail their successful application broad range transformations. Those include functionalization challenging C-H bonds beyond, giving an extensive catalogue valuable molecules. A critical comparison existing families, design, synthesis, complexation different metals also provided. In addition, future research directions are discussed further enhance performance CpX enantioselective catalysis.

Language: Английский

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Transition Metal Catalyzed Enantioselective C(sp²)–H Bond Functionalization

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(23), P. 13748 - 13793

Published: Nov. 12, 2020

Direct catalytic transformation of C–H bonds to new functionalities has provided a powerful strategy synthesize complex molecular scaffolds in straightforward way. Unstinting efforts the synthetic community have helped overcome long-standing major challenge regioselectivity by introducing directing group concept. However, full potential cannot be realized unless activated are stereochemically controlled. The enantioselective bond functionalization could provide an imperative tool for sustainable way synthesizing chiral scaffolds. Despite intrinsic challenges achieving stereocontrol, developed different tools order achieve stereoselective functionalization. In this review, we discuss remarkable recent advances emerging area C(sp2)–H highlight and opportunities, emphasizing techniques so far.

Language: Английский

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Diverse Approaches for Enantioselective C−H Functionalization Reactions Using Group 9 Cp^xM^III Catalysts

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(33), P. 7346 - 7357

Published: Jan. 29, 2020

Transition-metal-catalyzed C-H functionalization reactions with Cp*MIII catalysts (M=Co, Rh, Ir) have found a wide variety of applications in organic synthesis. Albeit the intrinsic difficulties achieving catalytic stereocontrol using these due to their lack additional coordination sites for external chiral ligands and conformational flexibility Cp ligand, enantioselective Group 9 metal triad Cp-type been intensively studied since 2012. In this minireview, progress according type catalyst used are summarized discussed. The development Cpx complexes thereof, artificial metalloenzymes, carboxylate-assisted activations, alkylations assisted by carboxylic acids or sulfonates, transient directing groups

Language: Английский

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A Strategy for Synthesizing Axially Chiral Naphthyl‐Indoles: Catalytic Asymmetric Addition Reactions of Racemic Substrates

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(42), P. 15104 - 15110

Published: Aug. 23, 2019

Abstract A new strategy for enantioselective synthesis of axially chiral naphthyl‐indoles has been established through catalytic asymmetric addition reactions racemic with bulky electrophiles. Under phosphoric acid catalysis, azodicarboxylates and o ‐hydroxybenzyl alcohols served as but reactive electrophiles that were attacked by C2‐unsubstituted naphthyl‐indoles, which underwent a dynamic kinetic resolution to afford two series in good yields (up 98 %) high enantioselectivities 98:2 er).

Language: Английский

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