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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Organocatalytic Asymmetric Synthesis of Indole-Based Chiral Heterocycles: Strategies, Reactions, and Outreach

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 53(2), P. 425 - 446

Published: Dec. 10, 2019

Indole-based chiral heterocycles constitute a class of important heterocyclic compounds that are found in numerous pharmaceuticals, functional materials, and catalysts or ligands. Catalytic asymmetric synthesis, for which the 2001 Nobel Prize Chemistry was awarded, has been demonstrated to be most efficient method accessing compounds. Therefore, catalytic synthesis indole-based attracted great interest from scientific community. However, strategies toward this goal rather limited, challenges remain field, such as metal contamination products, limited number platform molecules with versatile reactivity, reactions offer high step economy, atom excellent enantiocontrol. novel urgently needed. To achieve goal, our group developed series unique strategies, designing developing their corresponding organocatalytic access heterocycles. In Account, we describe efforts address remaining research field. Namely, have designed vinylindoles, indolylmethanols, arylindoles indole derivatives construction scaffolds structural diversity complexity. Based on reactivities these molecules, accomplished cycloaddition, cyclization, addition dearomatization economy Using wide range heterocycles, including five-membered seven-membered axially tetrasubstituted synthesized efficiency enantioselectivity. addition, investigated properties some bioactivities activities, showed potent anticancer activities promising catalysis. These results help elucidate potential applications drug development catalysts. The undoubtedly become will continue hot topic field catalysis synthesis. Our efforts, summarized not only open window future innovative but also inspire chemists worldwide confront prompt further advances.

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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Progresses in organocatalytic asymmetric dearomatization reactions of indole derivatives

Organic Chemistry Frontiers, Journal Year: 2020, Volume and Issue: 7(23), P. 3967 - 3998

Published: Jan. 1, 2020

This review summarizes the progresses in organocatalytic asymmetric dearomatization reactions of indole derivatives and their applications total synthesis natural products, gives some insights into challenging issues this research field.

Language: Английский

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Chiral Phosphoric Acid Catalyzed Atroposelective C−H Amination of Arenes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(17), P. 6775 - 6779

Published: Feb. 4, 2020

N-arylcarbazole structures are important because of their prevalence in natural products and functional OLED materials. C-H amination arenes has been widely recognized as the most efficient approach to access these structures. Conventional strategies involving transition-metal catalysts suffer from confined substrate generality requirement exogenous oxidants. Organocatalytic enantioselective C-N chiral axis construction remains elusive. Presented here is first organocatalytic strategy for synthesis novel axially frameworks by assembly azonaphthalenes carbazoles. This reaction accommodates broad scope gives atropisomeric N-arylcarbazoles good yields with excellent enantiocontrol. not only offers an alternative metal-catalyzed cross-coupling, but also brings about opportunities exploitation structurally diverse N-aryl atropisomers

Language: Английский

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Palladium‐Catalyzed Enantioselective Cacchi Reaction: Asymmetric Synthesis of Axially Chiral 2,3‐Disubstituted Indoles

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(5), P. 2105 - 2109

Published: Nov. 22, 2019

We report herein the first examples of a palladium-catalyzed enantioselective Cacchi reaction for synthesis indoles bearing chiral C2-aryl axis. In presence catalytic amount Pd(OAc)2 and (R,R)-QuinoxP* ligand, N-aryl(alkyl)sulfonyl-2-alkynylanilides with arylboronic acids under oxygen atmosphere afforded enantioenriched 2,3-disubstituted in high yields enantioselectivity. The indole ring is constructed de novo this process complexation-induced chirality transfer proposed to account observed

Language: Английский

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Atroposelective Access to Oxindole-Based Axially Chiral Styrenes via the Strategy of Catalytic Kinetic Resolution

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(37), P. 15686 - 15696

Published: Aug. 26, 2020

Atroposelective synthesis of axially chiral molecules has attracted substantial attention from chemists because the importance such molecules. However, catalytic asymmetric styrenes or vinyl arenes is underdeveloped and challenging due to low rotational barrier weak configurational stability Therefore, development powerful strategies for atroposelective great importance. In this work, we have accomplished first access oxindole-based by strategy kinetic resolution, offered two kinds styrene derivatives in good diastereoselectivities (up 94:6 dr) excellent enantioselectivities 98% ee) with high selectivity factors (S up 106). This not only provides easy but also offers a robust method synthesizing bisamide bearing both axial central chirality. More importantly, added new class members atropisomeric family, especially family styrenes.

Language: Английский

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Organocatalytic Atroposelective Synthesis of N−N Axially Chiral Indoles and Pyrroles by De Novo Ring Formation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(17)

Published: Jan. 26, 2022

Abstract The first highly atroposelective construction of N−N axially chiral indole scaffolds was established via a new strategy de novo ring formation. This makes use the organocatalytic asymmetric Paal–Knorr reaction well‐designed N ‐aminoindoles with 1,4‐diketones, thus affording ‐pyrrolylindoles in high yields and excellent atroposelectivities (up to 98 % yield, 96 ee). In addition, this is applicable for synthesis bispyrroles 97 More importantly, such heterocycles can be converted into organocatalysts applications catalysis, some molecules display potent anticancer activity. work not only provides but also offers members atropisomer family promising synthetic medicinal chemistry.

Language: Английский

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Catalytic Asymmetric Synthesis of Axially Chiral 3,3'‐Bisindoles by Direct Coupling of Indole Rings

Chinese Journal of Chemistry, Journal Year: 2022, Volume and Issue: 40(18), P. 2151 - 2160

Published: May 31, 2022

Comprehensive Summary A new strategy for the enantioselective synthesis of axially chiral 3,3'‐bisindoles was devised by direct coupling two indole rings. This makes use C3‐umpolung reactivity 2‐indolylmethanols, which enables catalytic asymmetric addition reaction 2‐indolylmethanols with rationally designed 2‐substituted indoles, thus constructing 3,3'‐bisindole scaffolds in overall excellent yields (up to 98%) high enantioselectivities 96 : 4 er). approach not only has overcome challenges five‐five‐membered heterobiaryls, but also represents a application catalysis. More importantly, this class can undergo variety post‐functionalizations give 3,3'‐bisindole‐based organocatalysts, have found their preliminary applications

Language: Английский

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