Enantioselective Synthesis of N−N Biaryl Atropisomers through Iridium(I)‐Catalyzed C−H Alkylation with Acrylates

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)

Published: May 4, 2023

Abstract Enantioselective synthesis of N−N biaryl atropisomers is an emerging area but remains underexplored. The development efficient in great demand. Herein, the construction through iridium‐catalyzed asymmetric C−H alkylation reported for first time. In presence readily available Ir precursor and Xyl‐BINAP, a variety axially chiral molecules based on indole‐pyrrole skeleton were obtained good yields (up to 98 %) with excellent enantioselectivity 99 % ee). addition, bispyrrole could also be synthesized enantioselectivity. This method features perfect atom economy, wide substrate scope, multifunctionalized products allowing diverse transformations.

Language: Английский

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Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(17), P. 10641 - 10727

Published: Aug. 28, 2023

Enantiomers, where chirality arises from restricted rotation around a single bond, are atropisomers. Due to the unique nature of origins their chirality, synthetic strategies access these compounds in an enantioselective manner differ those used prepare enantioenriched containing point arising unsymmetrically substituted carbon center. In particular stereodynamic transformations, such as dynamic kinetic resolutions, thermodynamic and deracemizations, which rely on ability racemize or interconvert enantiomers, promising set transformations optically pure late stage sequence. Translation approaches with atropisomers requires expanded toolbox for epimerization/racemization provides opportunity develop new conceptual framework synthesis compounds.

Language: Английский

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Catalytic atroposelective synthesis

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(5), P. 483 - 498

Published: April 30, 2024

Language: Английский

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Atroposelective catalysis

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 497 - 517

Published: June 18, 2024

Language: Английский

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Desymmetrization–Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18892 - 18898

Published: July 5, 2024

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated synthesis series chiral functionalized cyclopropanes with high yield, enantioselectivity, diastereoselectivity (44 examples, up 93% yield >99% ee). A possible mechanism involving cyclopropene desymmetrization Co-H species imine addition Co-alkyl was proposed. study provides novel route important extends frontier metallaphotoredox

Language: Английский

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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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Dynamic Kinetic Resolution of 2‐(Quinolin‐8‐yl)Benzaldehydes: Atroposelective Iridium‐Catalyzed Transfer Hydrogenative Allylation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(35)

Published: June 30, 2023

An atroposelective Ir-catalyzed dynamic kinetic resolution (DKR) of 2-(quinolin-8-yl)benzaldehydes/1-naphthaldehydes by transfer hydrogenative coupling allyl acetate is disclosed. The allylation reaction takes place with simultaneous installation central and axial chirality, reaching high diastereoselectivities excellent enantiomeric excesses when ortho-cyclometalated iridium-DM-BINAP used as the catalyst. racemization substrates occurs through a designed transient Lewis acid-base interaction between quinoline nitrogen atom aldehyde carbonyl group.

Language: Английский

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Expedient Synthesis of Axially and Centrally Chiral Diaryl Ethers via Cobalt-Catalyzed Photoreductive Desymmetrization

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4638 - 4647

Published: March 12, 2024

Axially chiral diaryl ethers make up a unique class of atropisomers bearing restricted rotation about the C–O bond. Methods for expedient synthesis axially ether-based structures have been largely underdeveloped. Herein, we developed an efficient metal-catalyzed desymmetrization strategy to unveil formation and centrally dual in high diastereo- enantioselectivity. The protocol leverages cobalt-catalyzed photoreductive enantioselective couplings dialdehyde alkyne deliver stereogenicity, ether scaffold is equipped with useful synthetic handles including formyl, hydroxyl, allyl groups, as has demonstrated carboxylic acid potential ligand asymmetric catalysis.

Language: Английский

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Atropisomeric Carboxylic Acids Synthesis via Nickel‐Catalyzed Enantioconvergent Carboxylation of Aza‐Biaryl Triflates with CO₂

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: March 26, 2024

Abstract Upgrading CO 2 to value‐added chiral molecules via catalytic asymmetric C−C bond formation is a highly important yet challenging task. Although great progress on the of centrally carboxylic acids has been achieved, construction axially with never reported date. Herein, we report first synthesis , which enabled by nickel‐catalyzed dynamic kinetic reductive carboxylation racemic aza‐biaryl triflates. A variety acids, are valuable but difficult obtain catalysis, generated in an enantioconvergent version. This new methodology features good functional group tolerance, easy scale‐up, facile transformation and avoids cumbersome steps, handling organometallic reagents using stoichiometric materials. Mechanistic investigations indicate process induced nickel catalysis.

Language: Английский

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Enantioselective Arylation of Sulfenamides to Access Sulfilimines Enabled by Palladium Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(37)

Published: June 27, 2024

Abstract Sulfur‐containing functional groups have garnered considerable attention due to their common occurrence in ligands, pharmaceuticals, and insecticides. Nevertheless, enantioselective synthesis of sulfilimines, particularly diaryl sulfilimines remains a challenging persistent goal. Herein we report highly enantio‐ chemoselective cross–coupling sulfenamides with aryl diazonium salt construct diverse S(IV) stereocenters by Pd catalysis. Bisphosphine ligands bearing sulfinamide play crucial role achieving high reactivity selectivity. This approach provides general, modular divergent framework for quickly synthesizing chiral sulfoximines that are otherwise access. In addition, the origins chemoselectivity enantioselectivity were extensively investigated using density theory calculations.

Language: Английский

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