Atroposelective Synthesis of Axially Chiral Diaryl Ethers by Copper-Catalyzed Enantioselective Alkyne–Azide Cycloaddition

ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 3475 - 3481

Опубликована: Фев. 21, 2024

Diaryl ethers are important structural motifs widely found in bioactive natural products, ligands, and catalysts. While there a variety of methods available to generate diaryl ethers, progress on the construction axially chiral has been slow. We report herein an atroposelective copper-catalyzed cycloaddition between bisalkynes azides. With indane-fused BOX ligand used, diverse array C–O atropisomers obtained with up 97% yield 99% ee. Control experiments showed that sequential enantioselective desymmetrization–kinetic resolution process is involved, former plays major role. In addition, asymmetric depletion observed for this catalytic synthesis by nonlinear effect studies. By thermal racemization experiments, rotational barrier axis 3aa calculated be 35.9 kcal/mol, which lays foundation its isolation, as well further applications.

Язык: Английский

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Atroposelective Synthesis of Axially Chiral Diaryl Ethers by N-Heterocyclic-Carbene-Catalyzed Sequentially Desymmetric/Kinetic Resolution Process

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(6), С. 4067 - 4073

Опубликована: Фев. 23, 2024

We describe herein an N-heterocyclic-carbene-catalyzed atroposelective synthesis of axially chiral diaryl ethers. Through a sequentially enantioselective desymmetric process and kinetic resolution process, the products could be constructed in good yields with excellent enantiopurities. Both alcohols phenols were compatible this catalytic system. The carboxylic acids derived from esters proven to potential ligands for asymmetric synthesis, example, Rh(III)-catalyzed C–H functionalization.

Язык: Английский

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Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes

ACS Catalysis, Год журнала: 2024, Номер 14(15), С. 11318 - 11331

Опубликована: Июль 15, 2024

Catalytic enantioselective borylation reactions of unsaturated bonds as powerful tools for the synthesis diverse chiral organoboron compounds have gained much attention and wide applications in various fields. However, atroposelective arylboration reaction with carbon–carbon triple 1,3-enynes to obtain axially 1,3-dienylboronates remains an elusive significant challenge. Hence, we develop a cooperative copper- palladium-catalyzed assemble plentiful function enriched single step from easily available 1,3-enynes, B2pin2, aryl bromides high levels chemo-, regio-, stereo-, atroposelectivity. The mild conditions lead good functional group tolerance, which is proven by broad substrate scope late-stage functionalizations bioactive or drug molecules. Moreover, can be scaled up, series further transformations achieved. It worth emphasizing that several olefin catalysts ligands axial chirality also synthesized through corresponding elaborations such products, explains transformative ability application potential 1,3-dienylboronates. mechanism experiment density theory (DFT) calculations revealed process copper palladium catalysis, indicating chemoselectivity regioselectivity boration are determined enyne insertion on copper, atroposelectivity controlled reductive elimination center. Meanwhile, calculation demonstrated distinct interactions between P═O C═O groups Pd Bpin center key transition state formation products varying configurations while employing identical configuration ligands.

Язык: Английский

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

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 2351 - 2358

Опубликована: Янв. 24, 2025

Язык: Английский

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Organocatalytic Atroposelective Hydroselenation of Alkynes To Access Axially Chiral Vinyl Selenides

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4051 - 4060

Опубликована: Фев. 20, 2025

Язык: Английский

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Copper‐Catalyzed Enantioselective and Regiodivergent Allylation of Ketones with Allenylsilanes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(44)

Опубликована: Сен. 5, 2023

Abstract We report herein a regiodivergent and enantioselective allyl addition to ketones with allenylsilanes through copper catalysis. With the combination of CuOAc, Josiphos‐type bidentate phosphine ligand PhSiH 3 , variety furnishes branched products in excellent enantioselectivities. The regioselectivity is completely reversed by employing P‐stereogenic BenzP*, affording linear enantioselectivities good Z ‐selectivities. ‐product could be converted E via catalytic geometric isomerization ‐alkene group. silyl group provide handle for downstream elaboration.

Язык: Английский

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Ligand-Controlled Regiodivergent Ring Expansion of Benzosilacyclobutenes with Alkynes en Route to Axially Chiral Silacyclohexenyl Arenes

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 21, 2024

A ligand-controlled regiodivergent and enantioselective ring expansion of benzosilacyclobutenes with internal naphthyl alkynes has been achieved by adjusting the ligand cavity size. The (

Язык: Английский

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Rhodium-Catalyzed Asymmetric Hydroselenation of 1-Alkynylindoles for Atroposelective Synthesis of Vinyl Selenoethers

ACS Catalysis, Год журнала: 2024, Номер 14(17), С. 13055 - 13064

Опубликована: Авг. 15, 2024

Catalytic asymmetric hydrofunctionalization of π-bonds has been extensively studied, but the alkynes that affords atropoisometric products remains heavily underexplored. We herein report [Rh(COD)OAc]2/Mg(NTf2)2-catayzed highly atroposelective hydroselenation two classes 1-alkynylindoles using selenophenols, where Mg(II) salt both activates Rh catalyst and provides a key NTf2 anion essential for catalytic activity enantioselectivity, affording C–N axially chiral trisubstituted olefins bear relatively low racemization barrier (ΔG‡ ∼ 27 kcal/mol). The system features high activity, mild reaction conditions, good functional group tolerance, regio-, (E)-, enantioselectivity. selenoether moiety in product framework can be readily functionalized to give synthetically useful products.

Язык: Английский

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Update Hydrometallation Group 4 (Si, Ge and Sn)

Elsevier eBooks, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Язык: Английский

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Rhodium(I)‐Catalyzed Asymmetric Hydroarylative Cyclization of 1,6‐Diynes to Access Atropisomerically Labile Chiral Dienes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(1)

Опубликована: Ноя. 16, 2023

Abstract Axially chiral open‐chained olefins are an underexplored class of atropisomers, whose enantioselective synthesis represents a daunting challenge due to their relatively low racemization barrier. We herein report rhodium(I)‐catalyzed hydroarylative cyclization 1,6‐diynes with three distinct classes arenes, enabling highly broad range axially 1,3‐dienes that conformationally labile (Δ G ≠ ( rac )=26.6–28.0 kcal/mol). The coupling reactions in each category proceeded excellent enantioselectivity, regioselectivity, and Z/E selectivity under mild reaction conditions. Computational studies the quinoline N ‐oxide system reveal proceeds via initial oxidative 1,6‐diyne give rhodacyclic intermediate, followed by σ‐bond metathesis between arene C−H bond Rh−C(vinyl) bond, subsequent C−C reductive elimination being enantio‐determining turnover‐limiting. DFT‐established mechanism is consistent experimental studies. coupled products ‐oxides undergo facile visible light‐induced intramolecular oxygen‐atom transfer, affording epoxides complete axial‐to‐central chirality transfer.

Язык: Английский

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