Organocatalytic diastereo- and atroposelective construction of N–N axially chiral pyrroles and indoles

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Янв. 15, 2024

Abstract The construction of N–N axially chiral motifs is an important research topic, owing to their wide occurrence in natural products, pharmaceuticals and ligands. One efficient method the atroposelective dihydropyrimidin-4-one formation. We present herein a direct catalytic synthesis atropisomers with simultaneous creation contiguous axial central chirality by oxidative NHC ( N -heterocyclic carbenes) catalyzed (3 + 3) cycloaddition. Using our method, we are able synthesize structurally diverse pyrroles indoles vicinal or bearing 2,3-dihydropyrimidin-4-one moiety moderate good yields excellent enantioselectivities. Further synthetic transformations obtained derivative products demonstrated. reaction mechanism origin enantioselectivity understood through DFT calculations.

Язык: Английский

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Atroposelective catalysis

Nature Reviews Chemistry, Год журнала: 2024, Номер 8(7), С. 497 - 517

Опубликована: Июнь 18, 2024

Язык: Английский

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Catalytic atroposelective synthesis of indolyl quinazolinones bearing N–N/C–C diaxes

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

Язык: Английский

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Atroposelective Synthesis of N–N Axially Chiral Indoles and Pyrroles via NHC-Catalyzed Diastereoselective (3 + 3) Annulation Strategy

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6965 - 6972

Опубликована: Апрель 18, 2024

The synthesis of N–N axially chiral molecules in the enantiopure form has emerged as an interesting research topic primarily due to significance and intricacy synthesizing these molecules, especially bearing heterocyclic motifs. Herein, we disclose a method for introduction axial chirality along with point center via N-heterocyclic carbene (NHC)-catalyzed atroposelective dihydropyridinone-containing indoles pyrroles. reaction follows (3 + 3) annulation approach by interception indole/pyrrole-derived enamines α,β-unsaturated aldehydes under oxidative NHC catalysis proceeding acylazoliums. indoles/pyrroles were formed mild conditions broad scope high selectivity. In addition, preliminary DFT studies rotational barrier products performed.

Язык: Английский

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Catalytic Asymmetric Synthesis of N−N Biaryl Atropisomers

Chemistry - A European Journal, Год журнала: 2023, Номер 30(2)

Опубликована: Окт. 18, 2023

Atropisomers have emerged as important structural scaffolds in natural products, drug design, and asymmetric synthesis. Recently, N-N biaryl atropisomers drawn increasing interest due to their unique structure relatively stable axes. However, its synthesis remains scarce compared well-developed C-C analogs. In this concept, we summarize the of including pyrrole-pyrrole, pyrrole-indole, indole-indole, indole-carbazole, during which a series synthetic strategies are highlighted. Also, evolution is briefly reviewed an outlook offered.

Язык: Английский

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Enantioselective Synthesis of “NO₂···NH” Hydrogen Bond-Stabilized C–N Axially Chiral Diarylamines

ACS Catalysis, Год журнала: 2024, Номер 14(2), С. 1183 - 1192

Опубликована: Янв. 9, 2024

Herein, N-nucleophilic tandem oxidation–N-arylation–oxidation reaction and C-nucleophilic bromination of substituted anilines have been developed using chiral phosphoric acid catalysis, enabling access to axially diarylamines. The key feature this strategy is that the "NO2···H–N" hydrogen bond was successfully introduced into acyclic diaryl secondary amines, which contain two potential contiguous atropisomeric C–N axes, stabilize one planar axial conformations. This methodology provided a series optically pure diarylamine atropisomers containing new type in good yields (up 99%) high enantiomeric ratios 99.5:0.5 e.r.). synthetic utility demonstrated through large-scale reactions transformations products. Plausible models were proposed explain enantioselectivity

Язык: Английский

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Atroposelective Synthesis of Axially Chiral Naphthylpyrroles by a Catalytic Asymmetric 1,3-Dipolar Cycloaddition/Aromatization Sequence

Organic Letters, Год журнала: 2024, Номер 26(4), С. 922 - 927

Опубликована: Янв. 24, 2024

A straightforward methodology for the enantioselective preparation of axially chiral 2-naphthylpyrroles has been developed. This protocol is based on a CuI/Fesulphos-catalyzed highly 1,3-dipolar cycloaddition an azomethine ylide followed by pyrrolidine alkylation and to pyrrole oxidation. The mild conditions employed in DDQ/blue light-mediated aromatization process facilitate effective central-to-axial chirality transfer affording corresponding pyrroles with high atroposelectivity.

Язык: Английский

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Enantioselective Nickel‐Catalyzed Denitrogenative Transannulation En Route to N−N Atropisomers

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(26)

Опубликована: Апрель 8, 2024

Nickel-catalyzed transannulation reactions triggered by the extrusion of small gaseous molecules have emerged as a powerful strategy for efficient construction heterocyclic compounds. However, their use in asymmetric synthesis remains challenging because difficulty controlling stereo- and regioselectivity. Herein, we report first nickel-catalyzed N-N atropisomers denitrogenative benzotriazones with alkynes. A broad range was obtained excellent regio- enantioselectivity under mild conditions. Moreover, density functional theory (DFT) calculations provided insights into reaction mechanism control.

Язык: Английский

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Enantioselective Synthesis of Benzimidazole Atropisomers Featuring a N‐N Axis^†

Chinese Journal of Chemistry, Год журнала: 2023, Номер 42(7), С. 711 - 718

Опубликована: Дек. 8, 2023

Comprehensive Summary Atroposelective synthesis of N‐N atropisomers is an emerging area but remains underexplored; in particular, the benzimidazole still unprecedented. Herein, first enantioselective via palladium‐catalyzed de novo construction skeleton presented. With readily available palladium catalyst and biphosphine ligand, a broad range nonbiaryl indole‐benzimidazole were conveniently accessed high yields with excellent enantioselectivities. Significantly, these showed great antitumor activity selectivity to breast cancer MCF‐7 cells. The simple catalytic system, substrate scope, enantioselectivity, good bioactivity make this approach highly attractive.

Язык: Английский

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Enantioconvergent and diastereoselective synthesis of atropisomeric hydrazides bearing a cyclic quaternary stereocenter through ternary catalysis

Chemical Science, Год журнала: 2024, Номер 15(33), С. 13240 - 13249

Опубликована: Янв. 1, 2024

The enantioselective and diastereoselective synthesis of atropisomeric hydrazides with defined vicinal central axial chirality via ternary catalysis in a one-pot process is reported.

Язык: Английский

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