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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Amide C–N bonds activation by A new variant of bifunctional N-heterocyclic carbene

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

Опубликована: Янв. 12, 2024

Abstract We report an organocatalyst that combines a triazolium N-heterocyclic carbene (NHC) with squaramide as hydrogen-bonding donor (HBD), which can effectively catalyze the atroposelective ring-opening of biaryl lactams via unique amide C–N bond cleavage mode. The free species attacks carbonyl, forming axially chiral acyl-azolium intermediate. Various amines be accessed by this methodology up to 99% ee and yield. By using mercaptan catalyst turnover agent, resulting thioester synthon transformed into several interesting atropisomers. Both control experiments theoretical calculations reveal crucial role hybrid NHC-HBD skeleton, activates H-bonding brings it spatially close centre. This discovery illustrates potential chimera demonstrates complementary strategy for activation manipulation.

Язык: Английский

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Chiral sulfide and achiral sulfonic acid cocatalyzed enantioselective electrophilic tandem selenylation semipinacol rearrangement of allenols

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 3, 2025

A highly enantioselective electrophilic selenylation/semipinacol rearrangement of allenols has been developed, which is enabled by the cooperative catalysis a chiral sulfide and an achiral sulfonic acid. The designed synthesized catalyst selenylating reagent play crucial role in enhancing both enantioselectivity reactivity. This approach exhibits excellent regio-, chemo-, enantioselectivity, providing access to diverse enantioenriched cyclopentanones featuring arylselenovinyl-substituted quaternary carbon stereocenter. Furthermore, these products can be transformed into synthetically valuable alkyne, vinyl bromide, aniline derivatives. Mechanistic studies reveal that combination acid not only facilitates formation catalytically active species, but also governs reaction. Meanwhile, density functional theory calculations disclose four hydrogen bond interactions π‧‧‧π interaction are responsible for observed enantioselectivity. Rearrangement reactions serve as steps syntheses biologically provide intellectual conceptual curiosities within broad field organic chemistry. Here, authors report allenols, catalysed Lewis base.

Язык: Английский

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Copper(I)‐Catalyzed Conjugate Addition/Enantioselective Protonation with Selenols and α‐Substituted α,β‐Unsaturated Thioamides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(24)

Опубликована: Апрель 22, 2023

Herein, a copper(I)-catalyzed asymmetric conjugate addition/protonation with selenols and α-substituted α,β-unsaturated thioamides is disclosed, which affords series of chiral selenides in high to excellent enantioselectivity. As for both thioamides, the reaction enjoys broad substrate scopes. The present catalytic system also successfully applied selenation β-substituted thioamides. A [Cu-(R,RP )-TANIAPHOS]-SePh species characterized by its 77 Se NMR spectra, gives chemical shift at δ 462 ppm. Moreover, {[Cu-(R)-TOL-BINAP]-SePh}2 X-ray analysis, confirms formation Cu-Se bond reaction. Finally, transformations thioamide group amine thioester are demonstrated be straightforward.

Язык: Английский

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Asymmetric Aminative Dearomatization of 2-Naphthols via Non-covalent N-Heterocyclic Carbene Catalysis

Organic Letters, Год журнала: 2023, Номер 25(13), С. 2323 - 2327

Опубликована: Март 30, 2023

Herein, successful utilization of non-covalent N-heterocyclic carbene (NHC) catalysis toward asymmetric aminative dearomatization naphthols is presented. The NHC-catalyzed process offers enantioselective synthesis cyclic enones possessing a nitrogen-containing α-quaternary stereocenter. reaction applies to various functionalized substrates including acid-labile groups and shown be scalable. Substrate activation via an O-H···NHC hydrogen-bonding interaction suggested based on the results obtained in mechanistic studies.

Язык: Английский

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N-Heterocyclic carbene (NHC) organocatalysis: from fundamentals to frontiers

Chemical Society Reviews, Год журнала: 2024, Номер unknown

Опубликована: Дек. 18, 2024

This tutorial review provides an overview of various important structural features and reactivity modes NHCs delves deep into the recent advances in NHC-organocatalysis.

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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Carbene-catalyzed enantioselective seleno-Michael addition as access to antimicrobial active Se-containing heterocycles

Science China Chemistry, Год журнала: 2024, Номер 67(7), С. 2199 - 2205

Опубликована: Май 28, 2024

Язык: Английский

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Metal-Free Enantioselective 1,4-Addition of Diarylphosphine Oxides to α,β-Unsaturated Carboxylic Esters

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(11), С. 7573 - 7578

Опубликована: Май 23, 2024

The catalytic asymmetric conjugate addition of phosphorus nucleophiles to unsaturated compounds, catalyzed by metallic or nonmetallic catalysts, has been extensively developed. However, the enantioselective transformations involving α,β-unsaturated carboxylic esters for constructing chiral c-p bonds have rarely reported, particularly in metal-free processes. In this study, we present a novel methodology 1,4-addition diarylphosphine oxides using classical oxazaborolidine catalysts. Remarkably high yields and enantioselectivities were obtained most products. Furthermore, these valuable serve as crucial intermediates that can be transformed into various derivatives including amides, acids, alcohols single step.

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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