Dynamic Kinetic Reductive Grignard-Type Addition for the Construction of Axial and Central Chirality

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1147 - 1157

Published: Jan. 3, 2025

This study describes a photoredox/cobalt dual-catalyzed asymmetric Grignard-type addition reaction, enabling the synthesis of axially chiral hexatomic (six–six) N-heterobiaryls bearing extra secondary alcohol unit via an efficient dynamic kinetic transformation racemic N-heterobiaryl triflate substrates. The conversion facilitated both photoredox and classical reductive reaction conditions exhibits good functional group tolerance, broad substrate scope, satisfactory stereoselectivity. Furthermore, control experiments density theory calculations provide preliminary mechanistic insights.

Language: Английский

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Atroposelective Synthesis of Pyridoindolones Bearing Two Remote Distinct C–N Axes through Cobalt-Catalyzed Enantioselective C–H Activation

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

Published: March 13, 2025

C–N axially chiral compounds represent an important class of atropisomers that are prevalent in bioactive and material molecules. Despite recent advances synthetic methodologies, the asymmetric construction featuring multiple axes has been rarely explored, significantly limiting their further applications. Herein, we report a novel atroposelective synthesis diaxially pyridoindolones both six–five six–six through cobalt-catalyzed C–H annulation. This approach demonstrates exceptional efficiency, yielding diverse array with excellent yields atroposelectivities (60 examples, up to >99% yield, ee, >20:1 dr). Mechanistic studies revealed stereochemistry were generated fixed simultaneously during cyclometalation step, along unexpected amplification effect. The practicality this protocol is underscored by successful gram-scale syntheses various transformations, including formation phosphine ligand. Notably, photoluminescence quantum (ΦF 0.99) positive solvatochromism observed, coupled significant chiroptical properties, underscoring potential applications these organic fluorescent materials.

Language: Английский

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Feature Papers in Catalysis in Organic and Polymer Chemistry

Catalysts, Journal Year: 2025, Volume and Issue: 15(1), P. 83 - 83

Published: Jan. 17, 2025

Catalysis plays a key role in both organic chemistry and polymer [...]

Language: Английский

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Stereoselective Synthesis of Atropisomeric Amides Enabled by Intramolecular Acyl Transfer

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

Published: Jan. 1, 2025

A stereoselective strategy to make C–N atropisomeric amides based on intramolecular acyl transfer via a tethered Lewis basic pyridine or tertiary amine group is reported.

Language: Английский

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Lewis Acid-Enabled Chemodivergent Cycloadditions of Donor–Acceptor Cyclopropanes with Indoline-2-Thiones

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

Published: Feb. 20, 2025

Lewis acid-enabled reactions of donor-acceptor cyclopropanes (DACs) with indoline-2-thiones are reported. The reaction exhibits tunable annulation depending on the acid and substituent at N1 indoline-2-thiones. With AlCl3 as 1-isopropylindoline-2-thiones reactants, a direct ring opening DACs, followed by intramolecular nucleophilic addition/dehydration takes place leading to formation dihydro-2H-thiepino[2,3-b]indoles in moderate good yields. Using Yb(OTf)3 promoter 1-unsubstituted (3 + 2) cycloaddition DACs accompanied sulfur rearrangement give 3-indolyl-4,5-dihydrothiophenes In addition, synthetic transformation 3-indolyl-4,5-dihydrothiophene sulfone indole-based axially chiral scaffolds further extends utility structural complexity.

Language: Английский

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Atroposelective [4+1] Annulation for the Synthesis of Isotopic Isoindolinones Bearing both Central and Axial Chirality

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

Published: Jan. 1, 2025

Isotopically chiral molecules have drawn much attention due to their practical applications in drug discovery. However, existing studies this area are mainly limited centrally and H/D exchange. Herein, we report a phosphoric acid-catalyzed atroposelective [4+1] annulation of ketoaldehydes 1H-indol-1-amines. By means strategy, series D- 18O-labeled atropisomers featuring both central axial chiralities synthesized with high enantioselectivities diastereoselectivities good excellent isotopic incorporation. Experimental density functional theory suggest that the reaction involves sequential condensation, cyclization isomerization cascade, which second step is enantio-determining process.

Language: Английский

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Enantioselective Synthesis of Planar/Multiple Chiral [n]Cyclophanes through Asymmetric Allylation

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Comprehensive Summary Planar‐chiral cyclophanes with carbon‐centered chirality are important targets in natural products and pharmaceuticals. However, synthesizing such planar chiral two stereogenic elements via a one‐step asymmetric reaction remains formidable challenge. Herein, we present an efficient kinetic resolution method for planar‐chiral [ n ]cyclophanes chirality. This is achieved through the enantioselective allylation of racemic aldehyde catalyzed by Bi(OAc) 3 phosphoric acid. The delivers multiple high yields excellent enantioselectivities, showcasing remarkable efficiency ( s factor up to 292). broad substrate scope, scalability, potential derivatization highlight value this methodology. DFT calculations have also been performed provide insights into origin experimentally observed diastereo‐ enantioselectivity reaction.

Language: Английский

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Nickel-Catalyzed Dynamic Kinetic Asymmetric Reductive Arylation of Aldehydes with Heterobiaryl Triflates

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 15, 2025

In this context, we report a nickel-catalyzed dynamic kinetic asymmetric reductive arylation of aldehydes with racemic heterobiaryl triflates, offering series axially chiral heterobiaryls bearing centrally secondary alcohol moiety in highly diastereo- and enantioselective manner. The simultaneous control both axial central stereogenic elements the products lies stereoselective nucleophilic addition configurationally labile hetereobiaryl nickel complex to formyl group aldehydes.

Language: Английский

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New pyrrolo[3,4-d] isoxazolidines hbrid with furan as multi-target antitumor agents and multi-target enzyme inhibitors: Synthesis and in silico study

Bioorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 108377 - 108377

Published: March 1, 2025

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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