Copper‐Catalyzed Desymmetric Alkyne–Azide Cycloaddition to Access Axially Chiral Biaryls

European Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Abstract Axially chiral biaryls are an important class of structural units widely used in natural product synthesis, drug design, and as ligands for asymmetric catalysis. Although significant progress has been made the synthesis axially biaryls, some them still limited to narrow substrate ranges, low efficiency, moderate stereocontrol. Herein, we describe a highly efficient route prepare atropisomeric with triazole alkyne modules through desymmetrization prochiral dialkynyl diaryls utilizing cyclobutyl‐bridge box conjunction copper salts. The process mild conditions, good functional‐group tolerance, can obtain wide array valuable biaryl derivatives excellent yields enantioselectivities.

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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Desymmetric esterification catalysed by bifunctional chiral N-heterocyclic carbenes provides access to inherently chiral calix[4]arenes

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: May 13, 2025

Language: Английский

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Ni-Catalyzed Desymmetric Radical Cross-Coupling Reaction to Access Axially Chiral Biaryls

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(18), P. 13860 - 13866

Published: Sept. 3, 2024

The synthesis of axially chiral biaryls continues to garner significant attention in the scientific community. In this work, we introduce a Ni-catalyzed desymmetrization strategy for prochiral dibromoarenes, conducted under mild reaction conditions and with good functional group tolerance. This method allows from readily available coupling partners, such as aldehydes, ethers, unactivated alkyl bromides. Moreover, has been successfully applied concise enantioenriched azulene-embedded [7]helicene, promising organic optoelectronics material.

Language: Английский

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Construction of Axially Chiral 4-Aminoquinolines by Cycloaddition and Central-to-Axial Chirality Conversion

Organic Letters, Journal Year: 2024, Volume and Issue: 26(46), P. 9984 - 9989

Published: Nov. 14, 2024

A two-step strategy has been established for the enantioselective synthesis of 4-aminoquinolines possessing axial chirality. This approach involves a chiral phosphoric acid-catalyzed cycloaddition, followed by DDQ oxidation step. The method offers efficient access to variety 1,1'-biaryl-2,2'-amino alcohol derivatives in excellent yields and enantioselectivities (up 98% yield 93% ee). Furthermore, synthetic transformation products was also investigated.

Language: Английский

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