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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Chiral phosphoric acid-catalyzed asymmetric dearomatization reactions

Chemical Society Reviews, Journal Year: 2019, Volume and Issue: 49(1), P. 286 - 300

Published: Dec. 12, 2019

We summarize in this review the recent development of chiral phosphoric acid (CPA)-catalyzed asymmetric dearomatization reactions.

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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Stereodivergent Synthesis of Tetrahydrofuroindoles through Pd‐Catalyzed Asymmetric Dearomative Formal [3+2] Cycloaddition

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(8), P. 2134 - 2138

Published: Jan. 13, 2018

A stereodivergent synthesis of tetrahydrofuroindoles through palladium-catalyzed asymmetric dearomative formal [3+2] cycloaddition nitroindoles with epoxybutenes was developed. The polarity the solvent found to play a key role in diastereoselectivity. In toluene, good excellent yields (70-99 %), diastereoselectivity (87/13->95/5 d.r.), and enantioselectivity (85/15-94/6 e.r.) were obtained, regardless properties substituents on nitroindoles. acetonitrile, different diastereoisomer produced (75-98 %) stereoselectivity (78/22-93/7 d.r., 93/7-99/1 e.r.). Mechanistic studies conducted illustrate origin diastereodivergency. kinetic experiments indicate that rate-determining step this reaction is solvents. ESI-MS also support existence palladium complex intermediates catalytic cycle reaction.

Language: Английский

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Phosphine‐Catalyzed Enantioselective Dearomative [3+2]‐Cycloaddition of 3‐Nitroindoles and 2‐Nitrobenzofurans

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(16), P. 5422 - 5426

Published: Feb. 12, 2019

Abstract Over the past years, metal‐catalyzed dearomative cycloaddition of 3‐nitroindoles and 2‐nitrobenzofurans have emerged as a powerful protocol to construct chiral fused heterocyclic rings. However, organocatalytic reaction these two classes heteroarenes has become long‐standing challenging task. Herein, we report first example phosphine‐catalyzed asymmetric [3+2]‐cycloadditio 2‐nitrobenzofurans, which provide new, facile, efficient for synthesis 2,3‐fused cyclopentannulated indolines dihydrobenzofurans by reacting with allenoates MBH carbonates, respectively through [3+2]‐cycloaddition.

Language: Английский

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Pd‐Catalyzed Dearomatization of Anthranils with Vinylcyclopropanes by [4+3] Cyclization Reaction

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(17), P. 5739 - 5743

Published: Feb. 27, 2019

Abstract Dearomatization of anthranils with vinylcyclopropanes (VCPs) by Pd‐catalyzed [4+3] cyclization reaction has been realized. In the presence a catalytic amount borane as an activator, bridged cyclic products were obtained in good to excellent yields stereoselectivities. By introducing chiral PHOX ligand ( L5 ), asymmetric dearomatization reactions proceeded enantioselectivity. Borane plays key role for reactivity, likely owing formation borane–anthranil complex which confirmed NMR experiments.

Language: Английский

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Recent advances in asymmetric reactions catalyzed by chiral phosphoric acids

Chinese Chemical Letters, Journal Year: 2018, Volume and Issue: 29(8), P. 1181 - 1192

Published: Feb. 13, 2018

Language: Английский

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Visible-Light-Promoted Cascade Alkene Trifluoromethylation and Dearomatization of Indole Derivatives via Intermolecular Charge Transfer

Organic Letters, Journal Year: 2018, Volume and Issue: 20(14), P. 4379 - 4383

Published: July 9, 2018

An intramolecular dearomatization of indole derivatives has been developed via an electron donor–acceptor complex formed between and Umemoto's reagent. Without the requirement any catalyst additive, diverse trifluoromethyl-substituted spiroindolenines bearing a quaternary stereogenic center were obtained in good yields (up to 90%) merely upon illumination two starting materials 1,2-dichloroethane solution at room temperature. This work provides facile access trifluoromethyl group enabled by visible light.

Language: Английский

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Catalytic asymmetric preparation of pyrroloindolines: strategies and applications to total synthesis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(10), P. 5985 - 6012

Published: Jan. 1, 2021

Pyrroloindolines are widely present in natural products. In this review, we summarize state-of-the-art of catalytic asymmetric synthesis pyrroloindolines, as well related applications to products total synthesis.

Language: Английский

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Atroposelective Synthesis of 3,3’‐Bisindoles Bearing Axial and Central Chirality: Using Isatin‐Derived Imines as Electrophiles

Chinese Journal of Chemistry, Journal Year: 2020, Volume and Issue: 38(6), P. 583 - 589

Published: Feb. 27, 2020

Summary of main observation and conclusion An atroposelective synthesis a new class 3,3’‐bisindoles bearing axial central chirality has been established via catalytic asymmetric addition reactions using isatin‐derived imines as electrophiles (23 examples, up to 80% yield, > 95 : 5 dr, 98 2 er). This approach takes advantage chiral phosphoric acid‐catalyzed dynamic kinetic resolution 2‐substituted nucleophilic such substrates with imines. In this approach, acted competent due their high reactivity bulky size, which provided an easy access axially 3,3'‐bisindoles incorporated biologically important 3‐aminooxindole unit. greatly expanded the generality applicability strategy for enantioenriched 3,3’‐bisindole derivatives both chirality.

Language: Английский

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