Palladium-catalyzed regio- and stereo-selective phosphination of cyclic biarylsulfonium salts to access atropoisomeric phosphines

Chemical Science, Journal Year: 2024, Volume and Issue: 15(18), P. 6943 - 6948

Published: Jan. 1, 2024

A Pd-catalyzed atroposelective phosphination of cyclic biarylsulfonium salts with HPAr 3 Ar 4 for straightforward synthesis chiral phosphines bearing a stereogenic axis or both and P-stereogenic center is reported.

Language: Английский

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Enantioselective Synthesis of Axially Chiral Alkylidenecycloalkanes via Copper-Catalyzed Functionalization of Acyl Allenols

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2351 - 2358

Published: Jan. 24, 2025

Language: Английский

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Dynamic kinetic resolution and dynamic kinetic asymmetric transformation of atropisomeric biaryls

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101329 - 101329

Published: March 1, 2025

Language: Английский

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Padlocking dihydrofurannulation for the control of small degree of helicity built on a fused-tetracyclic core

Chemical Science, Journal Year: 2024, Volume and Issue: 15(19), P. 7300 - 7307

Published: Jan. 1, 2024

Enantioselective construction of small molecules displaying a configurationally stable helical shape built on fused-tetracyclic core is daunting synthetic challenge even more pronounced when five-membered rings are incorporated in the structure. The resulting higher configurational lability strongly hampers their access, and therefore development new efficient methodologies timely highly desirable. In this context, we describe padlocking approach

Language: Английский

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Enantioselective Synthesis of Heteroatom‐Linked Non‐Biaryl Atropisomers

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 15, 2024

Atropisomers hold significant fascination, not only for their prevalence in natural compounds but also biological importance and wide-ranging applications as chiral materials, ligands, organocatalysts. While biaryl heterobiaryl atropisomers are commonly studied, the enantioselective synthesis of less abundant heteroatom-linked non-biaryl presents a formidable challenge modern organic synthesis. Unlike classical atropisomers, these molecules allow rotation around two bonds, resulting low barriers to enantiomerization through concerted bond rotations. In recent years discovery new configurationally stable rare scaffolds such aryl amines, ethers sulfones well innovative methodologies control configuration have been disclosed literature constitute topic this minireview.

Language: Английский

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1,5-Hydrogen atom transfer of α-iminyl radical cations: a new platform for relay annulation for pyridine derivatives and axially chiral heterobiaryls

Chemical Science, Journal Year: 2024, Volume and Issue: 15(20), P. 7502 - 7514

Published: Jan. 1, 2024

The exploitation of new reactive species and novel transformation modes for their synthetic applications have significantly promoted the development organic methodology, drug discovery, advanced functional materials. α-Iminyl radical cations, a class distonic ions, exhibit great potential synthesis valuable molecules. For generation, conjugate addition to α,β-unsaturated iminium ions represents concise yet highly challenging route, because

Language: Английский

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Catalytic stereodivergent and simultaneous construction of axial and point chirality

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(12), P. 3308 - 3319

Published: Jan. 1, 2024

An unprecedented ligand-enabled stereodivergent construction of both N–N axial and point chirality in a single step is reported.

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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Enantioconvergent synthesis of axially chiral amides enabled by Pd-catalyzed dynamic kinetic asymmetric aminocarbonylation

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 23, 2024

Atropisomeric biaryls bearing carbonyl groups have attracted increasing attention due to their prevalence in diverse bioactive molecules and crucial role as efficient organo-catalysts or ligands asymmetric transformations. However, preparation often involves tedious multiple steps, the direct synthesis via carbonylation has scarcely been investigated. Herein, we report an palladium-catalyzed enantioconvergent aminocarbonylation of racemic heterobiaryl triflates with amines dynamic kinetic transformation (DyKAT). This protocol features a broad substrate scope excellent compatibility for rapid construction axially chiral amides good high yields enantioselectivities. Detailed mechanistic investigations discover that base can impede intramolecular hydrogen bond-assisted axis rotation products, thus allowing success achieve enantioselectivity. Moreover, achieved be directly utilized N,N,N-pincer copper-catalyzed enantioselective formation C(sp3)-N C(sp3)-P bonds. Axially containing not only exist various drug candidates but also serve authors transformation.

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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