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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Organocatalytic dimensions to the C–H functionalization of the carbocyclic core in indoles: a review update

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(10), С. 2343 - 2365

Опубликована: Янв. 1, 2021

A review highlighting important research findings in remote C–H activation processes using effectual organocatalytic perspectives. The challenging indole carbocyclic ring positions were successfully accessed with proper regio- and stereocontrols.

Язык: Английский

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Organocatalytic Direct Asymmetric Indolization from Anilines by Enantioselective [3 + 2] Annulation

Organic Letters, Год журнала: 2021, Номер 23(21), С. 8434 - 8438

Опубликована: Окт. 26, 2021

We report the efficient syntheses of chiral tetrahydroindole pyrazolinones by asymmetric [3 + 2] cascade cyclizations (indolizations) simple aniline derivatives with pyrazolinone ketimines as 2C synthons. The phosphoric-acid-catalyzed system uses a concerted π–π interaction/dual H-bond control strategy to catalytically direct aniline, which undergoes highly chemo-, regio-, and enantioselective annulation, furnishing series optically active tetra-hydroindole two contiguous aza-quaternary carbon centers in excellent yields enantioselectivities. This method features relatively broad substrate scope for amines 2-naphthylamines highlights emerging value indolizations from amine sources organic synthesis.

Язык: Английский

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Chiral Phosphoric Acid-Catalyzed C6 Functionalization of 2,3-Disubstituted Indoles for Synthesis of Heterotriarylmethanes

Organic Letters, Год журнала: 2021, Номер 23(7), С. 2393 - 2398

Опубликована: Март 18, 2021

The direct regio- and enantioselective C6 functionalization of 2,3-disubstituted indoles with azadienes has been developed using chiral phosphoric acid as catalyst, providing a convenient approach to synthesize the optically active heterotriarylmethanes excellent yields, broad substrate scope, up 98% ee. Mechanistic studies revealed that N-alkylation would be reversible, could enabled.

Язык: Английский

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Base-Promoted Cobalt-Catalyzed Regio- and Enantioselective para-Friedel–Crafts Alkylation of Aniline Derivatives

Organic Letters, Год журнала: 2021, Номер 23(24), С. 9353 - 9359

Опубликована: Дек. 7, 2021

Herein we disclose a highly efficient enantioselective para-C-H alkylation of aniline derivatives promoted by base/Co/indeno-pybox ligand system. This methodology leads to the construction series enantioenriched bearing all-carbon quaternary stereocenters. In addition, several special biologically or medicinally active indoles are facilely synthesized our Co-catalyzed asymmetry synthesis method. Density functional theory calculations and experiment results suggest that (acac)- anion Co(acac)2 plays very important role in chiral control during nucleophilic reaction.

Язык: Английский

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Chiral phosphoric acid-catalyzed enantioselective aza-Friedel–Crafts reaction of naphthols and electron-rich phenols with 2-aryl-3H-indol-3-ones

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 21(3), С. 489 - 493

Опубликована: Дек. 8, 2022

Herein, we describe a challenging organocatalytic asymmetric aza- Friedel–Crafts reaction of naphthols/phenols with cyclic-ketimines attached to neutral functional group, achieving enantiomerically enriched chiral aminonaphthols.

Язык: Английский

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Aromatic C–H bond functionalization through organocatalyzed asymmetric intermolecular aza-Friedel–Crafts reaction: a recent update

Beilstein Journal of Organic Chemistry, Год журнала: 2023, Номер 19, С. 956 - 981

Опубликована: Июнь 28, 2023

The aza-Friedel–Crafts reaction allows an efficient coupling of electron-rich aromatic systems with imines for the facile incorporation aminoalkyl groups into ring. This has a great scope forming aza-stereocenters which can be tuned by different asymmetric catalysts. review assembles recent advances in reactions mediated organocatalysts. mechanistic interpretation origin stereoselectivity is also explained.

Язык: Английский

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Fe-Catalyzed Sequential C(sp³)–H/N–H Annulation of 2-Methylindoles with Ethyl Trifluoropyruvate at Room Temperature: Construction of Pyrrolo[1,2-α]indoles

Organic Letters, Год журнала: 2020, Номер 22(12), С. 4716 - 4720

Опубликована: Июнь 4, 2020

An efficient and benign iron-catalyzed room-temperature method was developed for direct sequential C(sp3)–H/N–H annulation to construct pyrroloindole scaffolds. This strategy features cheap readily available raw materials mild reaction conditions provides a green practical the one-pot rapid synthesis of wide range diversely functionalized pyrrolo[1,2-α]indoles.

Язык: Английский

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B(C6F5)3/CPA‐Catalyzed Aza‐Diels–Alder Reaction of 3,3‐Difluoro‐2‐Aryl‐3H‐indoles and Unactivated Dienes

Chemistry - A European Journal, Год журнала: 2024, Номер 30(34)

Опубликована: Апрель 16, 2024

Abstract Here we report B(C 6 F 5 ) 3/ CPA‐catalyzed enantioselective aza‐Diels–Alder reaction of 3,3‐difluoro‐2‐Aryl‐3 H ‐indoles with unactivated dienes to access chiral 10,10‐difluoro‐tetrahydropyrido[1,2‐ a ]indoles. This protocol allows the formation pyrazole‐based C2‐quaternary indolin‐3‐ones high enantioselectivities and regioselectivities. Moreover, gram‐scale synthesis ]indole skeleton was successfully achieved without any reduction in both yield enantioselectivity.

Язык: Английский

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Organocatalytic asymmetric tandem reaction for the enantioselective synthesis of chiral oxindoles to construct CyK dyes

Chem Catalysis, Год журнала: 2024, Номер unknown, С. 101188 - 101188

Опубликована: Ноя. 1, 2024

Язык: Английский

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