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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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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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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Recent advances in organocatalytic atroposelective reactions

Beilstein Journal of Organic Chemistry, Год журнала: 2025, Номер 21, С. 55 - 121

Опубликована: Янв. 9, 2025

Axial chirality is present in a variety of naturally occurring compounds, and becoming increasingly relevant also medicine. Many axially chiral compounds are important as catalysts asymmetric catalysis or have chiroptical properties. This review overviews recent progress the synthesis via organocatalysis. Atroposelective organocatalytic reactions discussed according to dominant catalyst activation mode. For covalent organocatalysis, typical enamine iminium modes presented, followed by N -heterocyclic carbene-catalyzed reactions. The bulk devoted non-covalent activation, where Brønsted acids feature most prolific catalytic structure. last part article discusses hydrogen-bond-donating other motifs such phase-transfer catalysts.

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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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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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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Synthesis of N–N Axially Chiral Pyrrolyl-oxoisoindolin via Isothiourea-Catalyzed Acylative Dynamic Kinetic Resolution

Organic Letters, Год журнала: 2024, Номер 26(29), С. 6179 - 6184

Опубликована: Июль 18, 2024

The development of methods for the asymmetric synthesis N-N axial chirality remains elusive and challenging. Here, we disclose a method construction axially chiral pyrrolyl-oxoisoindolins along with central via isothiourea (ITU)-catalyzed acylative dynamic kinetic resolution (DKR). Axial was introduced into DKR hemiaminals first time. This protocol features mild conditions excellent yields enantioselectivities.

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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Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Март 18, 2025

Chiral phosphoric acids (CPAs) have emerged as highly effective Brønsted acid catalysts in an expanding range of asymmetric transformations, often through novel multifunctional substrate activation modes. Versatile and broadly appealing, these benefit from modular tunable structures, compatibility with additives. Given the unique types noncovalent interactions (NCIs) that can be established between CPAs various reactants─such hydrogen bonding, aromatic interactions, van der Waals forces─it is unsurprising catalyst systems become a promising approach for accessing diverse chiral product outcomes. This review aims to provide in-depth exploration mechanisms by which impart stereoselectivity, positioning NCIs central feature connects broad spectrum catalytic reactions. Spanning literature 2004 2024, it covers nucleophilic additions, radical atroposelective bond formations, highlighting applicability CPA organocatalysis. Special emphasis placed on structural mechanistic features govern CPA-substrate well tools techniques developed enhance our understanding their behavior. In addition emphasizing details stereocontrolling elements individual reactions, we carefully structured this natural progression specifics broader, class-level perspective. Overall, findings underscore critical role catalysis significant contributions advancing synthesis.

Язык: Английский

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