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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Advances in organocatalytic asymmetric reactions of vinylindoles: powerful access to enantioenriched indole derivatives

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(11), P. 2643 - 2672

Published: Jan. 1, 2021

This review summarizes advances in vinylindole-based organocatalytic asymmetric reactions since 2008 and includes the applications of some methodologies total synthesis natural products, points out remaining challenges this research area.

Language: Английский

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Enantioselective three-component Ugi reaction catalyzed by chiral phosphoric acid

Science China Chemistry, Journal Year: 2019, Volume and Issue: 63(1), P. 47 - 54

Published: Oct. 22, 2019

Language: Английский

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Palladium-Catalyzed Asymmetric (4 + 2) Annulation of γ-Methylidene-δ-valerolactones with Alkenes: Enantioselective Synthesis of Functionalized Chiral Cyclohexyl Spirooxindoles

Organic Letters, Journal Year: 2021, Volume and Issue: 23(3), P. 745 - 750

Published: Jan. 21, 2021

An unprecedented asymmetric catalytic (4 + 2) annulation reaction of aryl-substituted γ-methylidene-δ-valerolactones (GMDVs) with isatin-derived para-quinone methides (p-QMs) has been developed under the catalysis palladium(0) and (S,S,S)-(−)-Xyl-SKP, offering a new approach for diastereo- enantioselective synthesis chiral cyclohexadienone-fused cyclohexyl spirooxindoles. Significantly, three highly congested contiguous tetrasubstituted carbon atoms embedded in bispirocyclic skeleton, which two are vicinal quaternary stereogenic centers, forged an effective selective manner (up to 99% yield, up 95% ee, >20/1 dr). The current represents first exploration forming six-membered carbocycles chemistry both GMDVs p-QMs.

Language: Английский

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Diastereoselective Synthesis of Tetrahydrospiro[carbazole-1,3′-indolines] via an InBr₃-Catalyzed Domino Diels–Alder Reaction

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(8), P. 5616 - 5629

Published: April 5, 2021

A simple InBr3-catalyzed domino reaction of indoles, phenylacetylenes, and various 3-methyleneoxindolines in toluene is described. This not only provided a convenient synthetic protocol for polysubstituted tetrahydrospiro[carbazole-1,3′-indolines] good yields but also gave completely different diastereoisomers the to that previously reported TfOH-catalyzed one-pot acetophenones, 3-methyleneoxindolines. Additionally, initially prepared 1,1′-bis(indolyl)phenylethanes with 3-phenacylideneoxindolines corresponding excellent diastereoselectivity. The mechanism involved sequential situ generation reactive dienophilic 3-alkenylindole, Diels–Alder reaction, Lewis acid controlled diastereoisomerization process.

Language: Английский

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Construction of chiral chroman scaffolds via catalytic asymmetric (4 + 2) cyclizations of para-quinone methide derivatives with 3-vinylindoles

Organic & Biomolecular Chemistry, Journal Year: 2020, Volume and Issue: 18(28), P. 5388 - 5399

Published: Jan. 1, 2020

The title reaction has been established in the presence of chiral phosphoric acid, affording chroman derivatives bearing an indole moiety high yields and with moderate to good stereoselectivities.

Language: Английский

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Asymmetric Organocatalytic [4 + 1] Annulations Involving a Polarity Reversal Process: A Tandem Catalytic Approach to Highly Functionalized Spiropyrazolone Derivatives

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 85(2), P. 594 - 602

Published: Dec. 2, 2019

A tandem catalytic strategy for the asymmetric synthesis of spirocyclopentanone pyrazolones bearing three contiguous stereocenters and two quaternary carbons with good stereoselectivities has been developed. This strategy, using as efficient C1 synthons involving a polarity reversal process, not only overcame energy barrier dearomatization process but also avoided nucleophilic addition hydroxy group in enol form tautomer. Futhermore, spirocyclopentanones could be transformed into spirocyclohexamide pyrazolone Lawesson reagent.

Language: Английский

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Four-Component Synthesis of 9H-Pyrimido[4,5-b]indoles Using Ammonium Iodide as the Nitrogen Source

Catalysts, Journal Year: 2023, Volume and Issue: 13(3), P. 623 - 623

Published: March 20, 2023

A four-component synthesis of 2-phenyl-9H-pyrimido[4,5-b]indoles was developed using indole-3-carboxaldehydes, aromatic aldehyde and ammonium iodide as the raw materials under transition-metal-free conditions. The pyrimidine ring formed in one pot through [4 + 2] annulation reaction. Four C–N bonds were promoted by iodine additives. This work is highlighted two iodides sole nitrogen source.

Language: Английский

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Harnessing structurally unbiasedortho-benzoquinone monoimine for biomimetic oxidative [4+2] cycloaddition with enamines

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(44), P. 5965 - 5968

Published: Jan. 1, 2020

Reported herein is the first catalytic oxidative [4+2] cycloaddition of 2-aminophenols with cyclic enamines. This biomimetic strategy expediently accommodates very labile structurally unbiased ortho-quinone monoimine intermediate for by controlling its formation rate, thus refraining from otherwise prerequisite steric or electronic stabilization and allowing efficient assembly various tricyclic 1,4-benzoxazines in a step atom economic fashion.

Language: Английский

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Enantioselectivity-Switchable Organocatalytic [4 + 2]-Annulation to Access the Spirooxindole–Norcamphor Scaffold

Organic Letters, Journal Year: 2021, Volume and Issue: 23(3), P. 963 - 968

Published: Jan. 22, 2021

An organocatalyzed enantiodivergent synthesis of a multifunctionalized spirooxindole-norcamphor scaffold via [4 + 2]-annulation between cyclicα, β-unsaturated ketone and methylene indolinones has been established. The presence CaCl2 in DMF could reverse the enantioselectivity to facilely deliver enantiomers corresponding spirooxindoles. Both spirooxindoles were obtained excellent yield diastereo-/enantioselectivity by employing one single prolinosulfonamide catalyst.

Language: Английский

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