Catalytic Asymmetric Diastereodivergent Synthesis of 2-Alkenylindoles Bearing both Axial and Central Chirality

Precision Chemistry, Год журнала: 2024, Номер 2(5), С. 208 - 220

Опубликована: Апрель 23, 2024

The catalytic asymmetric diastereodivergent synthesis of axially chiral 2-alkenylindoles was established via phosphoric acid-catalyzed addition reactions C3-unsubstituted with

Язык: Английский

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Pd-catalyzed asymmetric Larock reaction for the atroposelective synthesis of N─N chiral indoles

Science Advances, Год журнала: 2024, Номер 10(19)

Опубликована: Май 10, 2024

Atropisomeric indoles defined by a N─N axis are an important class of heterocycles in synthetic and medicinal chemistry material sciences. However, they remain heavily underexplored due to limited methods challenging stereocontrol over the short bonds. Here, we report highly atroposelective access axially chiral via asymmetric Larock reaction. This protocol leveraged powerful role phosphoramidite ligand attenuate common dissociation original reaction, forming with excellent functional group tolerance high enantioselectivity palladium-catalyzed intermolecular annulation between readily available o -iodoaniline alkynes. The multifunctionality prepared allowed diverse post-coupling transformations, affording broad array functionalized indoles. Experimental computational studies have been conducted explore reaction mechanism, elucidating enantio-determining rate-limiting steps.

Язык: Английский

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Atroposelective Synthesis of Planar‐Chiral Indoles via Carbene Catalyzed Macrocyclization

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(3)

Опубликована: Ноя. 28, 2023

Abstract Indole‐based planar‐chiral macrocycles are widely found in natural products and bioactive molecules. However, sharp contrast to the preparation of indole‐based axially chiral structures, enantioselective catalysis is still a formidable task so far. Here we report an N ‐heterocyclic carbene (NHC)‐catalyzed intramolecular atroposelective macrocyclization 3‐carboxaldehyde indole/pyrroles, featuring with broad substrate scope good functional group tolerance, allowing for rapid access diverse indole/pyrrole‐based various tether‐lengths (10–16 members) yields excellent enantioselectivities. Importantly, macrocyclic structures both planar axial chirality were directly efficiently obtained through this protocol enantioselectivities diastereoselectivities. In addition, these synthesized offer many possibilities chemists develop new catalysts or ligands, as well reactions.

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

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

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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Catalytic Atroposelective Synthesis of N–N Axially Chiral Indolylamides

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(17), С. 12559 - 12575

Опубликована: Авг. 27, 2024

The catalytic atroposelective synthesis of N–N axially chiral indolylamides was established via dynamic kinetic resolution, which makes use Lewis base-catalyzed asymmetric acylation N-acylaminoindoles as a new type platform molecule with anhydrides. By this strategy, series were synthesized in overall good yields (up to 98%) excellent enantioselectivities 99% ee). Moreover, some these display extent anticancer activity, demonstrates their potential application medicinal chemistry. Therefore, work has not only provided strategy for the monoaryl indoles but also offered member configurational stability and promising application, thereby solving challenges indoles.

Язык: Английский

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Atroposelective Synthesis of Planar‐Chiral Indoles via Carbene Catalyzed Macrocyclization

Angewandte Chemie, Год журнала: 2023, Номер 136(3)

Опубликована: Ноя. 28, 2023

Abstract Indole‐based planar‐chiral macrocycles are widely found in natural products and bioactive molecules. However, sharp contrast to the preparation of indole‐based axially chiral structures, enantioselective catalysis is still a formidable task so far. Here we report an N ‐heterocyclic carbene (NHC)‐catalyzed intramolecular atroposelective macrocyclization 3‐carboxaldehyde indole/pyrroles, featuring with broad substrate scope good functional group tolerance, allowing for rapid access diverse indole/pyrrole‐based various tether‐lengths (10–16 members) yields excellent enantioselectivities. Importantly, macrocyclic structures both planar axial chirality were directly efficiently obtained through this protocol enantioselectivities diastereoselectivities. In addition, these synthesized offer many possibilities chemists develop new catalysts or ligands, as well reactions.

Язык: Английский

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Rhodium-Catalyzed Regioselective [4 + 2] Cycloaddition of Ynamines and 2-(Cyanomethyl)phenylboronates

Organic Letters, Год журнала: 2024, Номер 26(31), С. 6586 - 6590

Опубликована: Июль 30, 2024

A rhodium-catalyzed [4 + 2] cycloaddition of ynamines and 2-(cyanomethyl)phenylboronates has been developed, leading to efficient excellent regioselective synthesis valuable indole-linked aromatic compounds in a concise flexible approach. Interestingly, this strategy was successful the construction C···N axially chiral indoles with high enantiocontrol by introduction new phosphoramidite ligand (Xie-Phos).

Язык: Английский

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Asymmetric Rh‐Catalyzed [2+2+2] Cycloaddition: Synthesis of N‐Alkenylindoles with both Axial and Central Chirality

ChemCatChem, Год журнала: 2024, Номер unknown

Опубликована: Сен. 3, 2024

Abstract Axially chiral indoline‐based scaffolds are virtually universal in biological and pharmaceutical compounds. In this study, we demonstrate the Rh‐catalyzed asymmetric [2 + 2 2] cycloaddition of 1,6‐enynes with steric hindered N‐ alkynyl indoles, which enables simultaneous construction both axial central chirality, containing a quaternary carbon center, one step. Notable features these reactions include excellent chemo‐, regio‐, diastereo‐ enantioselectivity, 100% atom‐economy, easily available SEGPHOS ligand, mild conditions.

Язык: Английский

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