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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Design and Organocatalytic Asymmetric Synthesis of Indolyl-Pyrroloindoles Bearing Both Axial and Central Chirality

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 88(12), P. 7684 - 7702

Published: Nov. 23, 2022

An axially chiral indolyl-pyrroloindole scaffold, a new member of indole-based scaffolds, has been designed, and the catalytic asymmetric construction this scaffold established by strategy organocatalytic (2 + 3) cycloaddition 3,3'-bisindoles with isoindolinone-based propargylic alcohols. By approach, series derivatives bearing both axial chirality central were synthesized in high yields excellent diastereo- enantioselectivities (up to 95% yield, 91:9 dr, 99% ee). This reaction not only realizes first n) as 1,2-dinucleophiles but also provides for atroposelective scaffolds five-five-membered rings, thus solving challenges constructing class scaffolds.

Language: Английский

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Dual Catalytic C(sp²)–H Activation of Azaheterocycles toward C–N Atropisomers

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3700 - 3710

Published: Feb. 14, 2025

Language: Английский

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Asymmetric Allylic Substitution‐Isomerization for the Modular Synthesis of Axially Chiral N‐Vinylquinazolinones

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 16, 2023

Abstract Axially chiral N ‐substituted quinazolinones are important bioactive molecules, which presented in many synthetic drugs. However, most strategies toward their atroposelective synthesis mainly limited to the axially arylquinazolinone frameworks. The development of modular methods access diverse quinazolinone‐based atropisomers remains scarce and challenging. Herein, we report regio‐ ‐vinylquinazolinones via strategy asymmetric allylic substitution‐isomerization. catalysis system utilized both transition‐metal organocatalysis efficiently afford trisubstituted tetrasubstituted ‐vinylquinazolinone atropisomers, respectively. With meticulous design β‐substituted substrates, Z ‐ E ‐tetrasubstituted were obtained good yields high enantioselectivities.

Language: Английский

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Photoredox Catalytic Deracemization Enabled Enantioselective and Modular Access to Axially Chiral N‐Arylquinazolinones

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 24, 2024

Visible light-driven photocatalytic deracemization is highly esteemed as an ideal tool for organic synthesis due to its exceptional atom economy and synthetic efficiency. Consequently, successful instances of allenes have been established, where the activated energy photosensitizer should surpass that substrates, representing intrinsic requirement. Accordingly, this method not applicable axially chiral molecules with significantly high triplet energies. In study, we present a photoredox catalytic approach enables efficient valuable yet challenging-to-access 2-azaarene-functionalized quinazolinones. The substrate scope extensive, allowing both 3-axis unmet 1-axis assembly through facile oxidation diverse central 2,3-dihydroquinazolin-4(1H)-ones can be easily prepared achieve enantiomer enrichment via deracemization. Mechanistic studies reveal importance selection in attaining excellent chemoselectivity highlight indispensability Brønsted acid enabling enantioselective protonation accomplish

Language: Английский

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Copper‐Catalyzed Asymmetric Arylation of α‐Substituted Cyanoacetates Enabled by Chiral Amide Ligands

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 23, 2023

The (S)-nobin-embodied picolinamide and L-hydroxyproline-derived amide are effective ligands for Cu-catalyzed enantioselective coupling reaction of (hetero)aryl iodides with α-alkyl substituted cyanoacetates. This arylation gave α-(heteroaryl)-α-alkyl cyanoacetates in good to excellent enantioselectivities (up 95 % ee). A variety functionalized alkyl groups could be introduced the quaternary center therefore provided a valuable tool preparing enantioenriched compounds an all-carbon tethered convertible functional groups. size both ester was proven as key factor asymmetric induction.

Language: Английский

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Recent Advances in Catalytic Desymmetrization for the Synthesis of Axially Chiral Biaryls

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: June 7, 2024

Abstract Atropisomeric compounds have been discovered in pharmaceuticals and materials science, their enantioselective syntheses gained tremendous attention. Among strategies for catalytic atroposelective synthesis, desymmetrization provides robust straightforward approaches to axially chiral biaryls. Due the relative ease of substrate design compared other strategies, has emerged as a pivotal stage converting fascinating chemistry into its counterpart, despite challenges such formation achiral products by subsequent reactions long distance between reaction site stereogenic axis. This review offers comprehensive overview recent advancements using organo‐ metal catalysts, addressing solutions, aims provide insights future developments this field.

Language: Английский

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Atroposelective Chan–Evans–Lam Amination

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(16)

Published: Jan. 5, 2024

The synthetic control of atropoisomerism along C-N bonds is a major challenge, and methods that allow atroposelective bond formation are rare. This problem because each atropoisomer can feature starkly differentiated biological properties. Yet, among the three most practical applicable classical amination available: 1) Cu-catalyzed Ullmann-Goldberg reaction, 2) Pd-catalyzed Buchwald-Hartwig 3) Chan-Evans-Lam none has truly been rendered at newly formed bond. first ever herein described with simple copper catalyst designed PyrOx chiral ligand. method should find important applications in asymmetric synthesis, particular for medicinal chemistry.

Language: Английский

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Design Approaches That Utilize Ionic Interactions to Control Selectivity in Transition Metal Catalysis

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

The attractive force between two oppositely charged ions can constitute a powerful design tool in selective catalysis. Enzymes make extensive use of ionic interactions alongside variety other noncovalent interactions; recent years have seen synthetic chemists begin to seriously explore these catalyst designs that also incorporate reactive transition metal. In isolation, single interaction exhibits low directionality, but many successful systems they exist additional which provide high degree organization at the selectivity-determining state. Even situations with key interaction, directionality is not always detrimental, and even be advantageous, conferring generality catalyst. This Review explores approaches utilize control selectivity metal It divided into halves: first, occurs outer sphere complex, using ligand or bound an anion; second, bears formal charge, associated counterion.

Language: Английский

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Enantioselective Desymmetrization of Biaryls via Cooperative Photoredox/Brønsted Acid Catalysis and Its Application to the Total Synthesis of Ancistrobrevolines

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 5, 2025

Photoredox catalysis has emerged as a powerful tool for forming and breaking chemical bonds, further taking hold with its integration asymmetric catalysis. While the dual-catalytic approach led to successful examples of control stereogenic centers, axes remained underexplored. In this study, an acylimine intermediate was generated through photoredox catalysis, symmetric substrate, 2-arylresorcinol, desymmetrized aid chiral phosphoric acid Using approach, center axis were successfully controlled provide natural-product-driven compound. The origins enantioselectivity diastereoselectivity investigated density functional theory study four possible enantiodetermining transition states. Consequently, first total syntheses ring-contracted naphthylisoquinoline alkaloid ancistrobrevolines A B accomplished concisely. This provides not only novel methodology strategy synthesize alkaloids but also direction advance catalytic research synthesis studies.

Language: Английский

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