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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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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N-Heterocyclic Carbene-Catalyzed Atroposelective Synthesis of N–N Axially Chiral 3-Amino Quinazolinones

ACS Catalysis, Год журнала: 2023, Номер 13(13), С. 8752 - 8759

Опубликована: Июнь 16, 2023

Although the atroposelective synthesis of biaryls and related compounds bearing axially chiral C–C bonds is well-known, C–N bond-containing relatively less explored, construction N–N has received only scant attention. Demonstrated herein N-heterocyclic carbene (NHC)-catalyzed selective amidation reaction, leading to 3-amino quinazolinones. The NHC-catalyzed reaction quinazolinones containing a free N–H moiety with α,β-unsaturated aldehydes under oxidative conditions furnished atropisomeric quinazolinone derivatives mild broad scope. Preliminary studies on experimental density functional theory-based rotational barrier determination are also presented.

Язык: Английский

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Enantioselective Synthesis of Axially Chiral Diaryl Ethers via NHC Catalyzed Desymmetrization and Following Resolution

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(4)

Опубликована: Ноя. 29, 2023

Axially chiral diaryl ethers are present in numerous natural products and bioactive molecules. However, only few catalytic enantioselective approaches have been established to access ether atropisomers. Herein, we report the N-heterocyclic carbene-catalyzed synthesis of axially via desymmetrization prochiral 2-aryloxyisophthalaldehydes with aliphatic alcohols, phenol derivatives, heteroaromatic amines. This reaction features mild conditions, good functional group tolerance, broad substrate scope excellent enantioselectivity. The utility this methodology is illustrated by late-stage functionalization, gram-scale synthesis, diverse enantioretentive transformations. Control experiments DFT calculations support association NHC-catalyzed following kinetic resolution enhance

Язык: Английский

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Synthesis of axially chiral diaryl ethers via NHC-catalyzed atroposelective esterification

Chemical Science, Год журнала: 2024, Номер 15(12), С. 4564 - 4570

Опубликована: Янв. 1, 2024

We present NHC-catalyzed atroposelective esterification of prochiral dialdehydes, delivering enantioenriched axially chiral diaryl ethers. Matched kinetic resolutions amplify the enantioselectivity by removing minor enantiomers via over-functionalization.

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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An Assembly of Pyrano[3,2‐b]indol‐2‐ones via NHC‐Catalyzed [3 + 3] Annulation of Indolin‐3‐ones with Ynals^†

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(13), С. 1487 - 1492

Опубликована: Март 10, 2024

Comprehensive Summary We report herein an unprecedented N ‐heterocyclic carbene‐catalyzed formal [3 + 3] annulation of ynals with ‐Ts indolin‐3‐ones under the oxidation condition affording functionalized pyrano[3,2‐ b ]indol‐2‐ones. The alkynyl acylazoliums via combination a carbene in presence oxidate proved to be important intermediates for success this transformation. This method features broad substrate scope and mild conditions, including axially chiral skeletons suitable substitutions.

Язык: Английский

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Copper-catalysed asymmetric annulation of yne-allylic esters with amines to access axially chiral arylpyrroles

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

Опубликована: Авг. 10, 2024

The construction of atropisomers with 1,2-diaxes, while maintaining high enantiocontrol, presents a significant challenge due to the dynamic nature steric hindrance at ortho-aryl substituents. Although various catalytic asymmetric methods have been developed for accessing axially chiral arylpyrroles, synthesis arylpyrroles 1,2-diaxes in manner has remained rare. Herein, authors report diverse and C-C C-N axes through copper-catalysed asymmetirc [4 + 1] annulation yne-allylic esters arylamines via remote stereocontrol strategy. This approach provides facile access broad range heterobiaryl (67 examples) excellent enantioselectivities, each bearing one or two C-C/C-N axes, demonstrating its versatility efficiency. utility this methodology is further highlighted by transformation product into phosphine ligand, thioureas use catalysis.

Язык: Английский

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Recent Advances in NHC‐Catalyzed Chemoselective Activation of Carbonyl Compounds

Chemistry - An Asian Journal, Год журнала: 2024, Номер 19(9)

Опубликована: Март 7, 2024

N-Heterocyclic carbenes (NHCs) catalysts have been employed as effective tools in the development of various reactions, which made notable contributions developing diverse reaction modes and generating significant functionalized molecules. This review provides an overview recent advancements chemo- regioselective activation different aldehydes using NHCs, categorized into five parts based on modes. A brief conclusion outlook is provided to stimulate novel for accessing functional

Язык: Английский

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N-Heterocyclic Carbene-Catalyzed Formal Intramolecular [3 + 2] Annulations of Cyclohexadienone-Tethered Ynals

Organic Letters, Год журнала: 2024, Номер 26(17), С. 3552 - 3556

Опубликована: Апрель 19, 2024

A formal [3 + 2] annulation of cyclohexadienone-tethered ynals is enabled by an N-heterocyclic carbene (NHC) catalyst, affording a tricyclo[6.2.1.04,11]undecane framework. This study represents the first demonstration using C═C double bonds as reaction partner in NHC-catalyzed ynals. strategy characterized mild conditions and 100% atom economy well high catalytic performance efficiency.

Язык: Английский

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