Enantioselective synthesis of molecules with multiple stereogenic elements

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(22), P. 11165 - 11206

Published: Jan. 1, 2024

This review explores the fascinating world of molecules featuring multiple stereogenic elements, unraveling different strategies designed over years for their enantioselective synthesis.

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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Enantioselective Synthesis of Axially and Centrally Chiral Styrenes via Nickel-Catalyzed Desymmetric Hydrocyanation of Biaryl Dienes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3867 - 3871

Published: May 1, 2024

Herein, a highly regio-, enantio-, and diastereoselective nickel-catalyzed desymmetric hydrocyanation of biaryl dienes for the simultaneous construction axial central chiralities is presented, which offers convenient approach to variety tirenes containing union an axially chiral centrally α-chiral nitrile under mild conditions using commercially available catalyst. The synthetic utility highlighted by development novel phosphine ligand biphenyl-based diene their potential applications in field asymmetric catalytic reactions.

Language: Английский

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Enantioselective Synthesis of Axially Chiral Diaryl Ethers through Chiral Phosphoric Acid-Catalyzed Desymmetric Acylation with Azlactones

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6667 - 6673

Published: April 16, 2024

C–O axially chiral diaryl ethers play important roles in natural products and bioactive molecules, but because of the low rotational barrier strict steric hindrance requirements, catalytic asymmetric construction still remains a challenge. Herein, we devised strategy employing achiral azlactone for desymmetrization prochiral diamines under catalysis phosphoric acid. The targeted were obtained very good yields (up to 98%) high enantioselectivities >99.5:0.5 er). synthetic utility was demonstrated through large-scale reaction transformations products. Moreover, DFT calculations conducted probe origins enantioselectivity.

Language: Английский

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Catalytic Asymmetric C–H Activation/Cyclization of Sulfoximines with Sulfoxonium Ylides by a Chiral η⁶-Benzene Ruthenium(II) Catalyst

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17398 - 17404

Published: Nov. 12, 2024

Chiral η6-benzene ruthenium(II) (BenRuII)-catalyzed asymmetric C–H activations are challenging and rarely seen in the literature. Herein, activation/cyclization of sulfoximines with sulfoxonium ylides catalyzed by chiral BenRuII catalyst derived from (S)-H8–BINOL is described. It provides efficient access to various sulfur-chiral 1,2-benzothiazine 1-oxides high yields enantioselectivities (up 99% yield 98% ee). Kinetic resolution racemic was also feasible. The reaction mechanism studied tool H/D exchange kinetic isotope effect. metallacycle revealing origin induction prepared, characterized, proved effective for model reaction. This work demonstrates great potential catalysts activation.

Language: Английский

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Recent progress in visible light‐driven halogenation: Chlorination, bromination, and iodination

Bulletin of the Korean Chemical Society, Journal Year: 2024, Volume and Issue: 45(9), P. 738 - 758

Published: Sept. 1, 2024

Abstract Halogenation is one of the most important transformations in organic synthesis. Halogenated compounds are employed many reactions to prepare useful molecules. Many methods have been developed introduce halogens into different compounds. Visible light‐mediated efficient, low‐toxic, and mild‐condition applied for various chemistry transformations. Remarkably, there has an increasing development application visible light‐induced halogenation recent years. Herein, we present a comprehensive summary including chlorination, bromination, iodination under light irradiation since 2020.

Language: Английский

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Construction of axially chiral molecules enabled by photoinduced enantioselective reactions

Chemical Science, Journal Year: 2024, Volume and Issue: 15(32), P. 12636 - 12643

Published: Jan. 1, 2024

Axially chiral molecular scaffolds are widely found in pharmaceutical molecules, functionalized materials, and ligands. The synthesis of these compounds has garnered considerable interest from both academia industry. construction such enabled by transition metal catalysis organocatalysis under thermodynamic conditions, been extensively studied well-reviewed. In recent years, photoinduced enantioselective reactions have emerged as powerful methods for the catalytic axial chirality. this review, we provide an overview various synthetic strategies chirality, with a specific focus on reaction design mechanisms. Additionally, discuss limitations current highlight future directions field.

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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Catalytic Atroposelective Construction of Diarylethers and Diarylamines

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7891 - 7911

Published: April 29, 2025

Language: Английский

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Evolution in the asymmetric synthesis of biaryl ethers and related atropisomers

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(54), P. 6837 - 6846

Published: Jan. 1, 2024

Axially chiral biaryl ethers and related compounds hold valuable potential in natural products, medicinal chemistry, catalysis; however, their asymmetric syntheses have always been overlooked compared to other biaryl/hetero-biaryl atropisomers. Unlike the later class molecules bearing a single axis, former category possesses unique type of atropisomerism two axes. Due great importance diverse research domains, catalytic atropselective ether synthesis has recently witnessed an upsurge. This highlight article provides elaborated view on developments synthetic methods that explored achieve dual axial chirality scaffolds.

Language: Английский

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