Expeditious entry into carbocyclic and heterocyclic spirooxindoles

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(29), С. 5651 - 5693

Опубликована: Янв. 1, 2022

Recent advances in the chemistry of base-, metal-, nano-metal and organo-catalyst mediated achiral chiral versions structurally diverse pharmaceutically relevant spirooxindoles are gently reviewed.

Язык: Английский

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Regiodivergent Organocatalytic Reactions

Catalysts, Год журнала: 2021, Номер 11(8), С. 1013 - 1013

Опубликована: Авг. 22, 2021

Organocatalysts are abundantly used for various transformations, particularly to obtain highly enantio- and diastereomeric pure products by controlling the stereochemistry. These applications of organocatalysts have been topic several reviews. emerged as one very essential areas research due their mild reaction conditions, cost-effective nature, non-toxicity, environmentally benign approach that obviates need transition metal catalysts other toxic reagents. Various types including amine catalysts, Brønsted acids, Lewis bases such N-heterocyclic carbene (NHC) cinchona alkaloids, 4-dimethylaminopyridine (DMAP), hydrogen bond-donating gained renewed interest because regioselectivity. In this review, we present recent advances in regiodivergent reactions governed organocatalysts. Additionally, briefly discuss pathways achieving changes conditions solvents, additives, or temperature.

Язык: Английский

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Catalyst-Controlled Switchable (5 + 4)/(3 + 4) Cycloadditions for the Divergent Synthesis of Pyrazole-Fused Seven- and Nine-Membered Heterocycles

ACS Catalysis, Год журнала: 2023, Номер 13(16), С. 10694 - 10704

Опубликована: Авг. 1, 2023

Developing diversity-oriented synthetic approaches for medium-sized rings is of great interest, and the divergent synthesis with different ring sizes poses a challenging task. In this study, we present catalyst-controlled switchable (5 + 4)/(3 4) cycloaddition strategy seven- nine-membered heterocycles. Utilizing two 4-aminopyridine Lewis base catalysts, pyrazole-fused benzazepines or benzoxazonines can be efficiently assembled from same substrates. These products exhibit good stability without interconversion under reaction conditions elevated temperatures. The origin chemoselectivity was elucidated by means computational studies involving DFT calculations, distortion/interaction analysis, noncovalent interaction analysis.

Язык: Английский

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Recent Advances in Nucleophilic Lewis Base‐Catalyzed Cycloadditions for Synthesis of Spirooxindoles

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(24), С. 4412 - 4439

Опубликована: Ноя. 16, 2023

Abstract Spirooxindoles are privileged scaffolds in diverse bioactive natural products and pharmaceuticals, significant achievements for the construction of these molecules have thus been made past years. Among them, organocatalysis, particular, nucleophilic Lewis base catalysis, has recently emerged as an efficient reliable method preparation valuable functionalized spirooxindoles. According to different kinds catalysts, we summarize classify three catalytic strategies; tertiary amine‐catalyzed cycloadditions, NHC‐catalyzed phosphine‐catalyzed respectively. Through methods, potential spirooxindole skeletons owning various functional groups can be produced enrich small organic molecule library. In this review, describe a comprehensive updated advances cycloaddition reactions Meanwhile, related mechanism application annulation strategies product total synthesis will highlighted detail.

Язык: Английский

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Modular synthesis of 1,4-diketones through regioselective bis-acylation of olefins by merging NHC and photoredox catalysis

Chinese Chemical Letters, Год журнала: 2023, Номер 34(11), С. 108271 - 108271

Опубликована: Март 2, 2023

Язык: Английский

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A review on solvent-controlled stereodivergent catalysis

Tetrahedron, Год журнала: 2023, Номер 150, С. 133754 - 133754

Опубликована: Ноя. 25, 2023

Язык: Английский

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Organocatalytic atroposelective synthesis of naphthoquinone thioglycosides from aryl-naphthoquinones and thiosugars

Chemical Communications, Год журнала: 2023, Номер 59(47), С. 7279 - 7282

Опубликована: Янв. 1, 2023

In this study, we report an organocatalytic formal coupling strategy for aryl-naphthoquinones with thiosugars that provides straightforward access to the axially chiral naphthoquinone thioglycoside excellent stereoselectivity. Mechanistic studies revealed key role of H-bonding in stereochemical recognition. The reaction pathway involves atroposelective addition, followed by stereoretentive oxidation hydroquinone intermediate.

Язык: Английский

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Construction of Cyclopentanes Consisting of Five Stereocenters via NHC-Catalyzed Cascade Reactions of Enals with Oxindole-Dienones

Organic Letters, Год журнала: 2023, Номер 25(47), С. 8445 - 8450

Опубликована: Ноя. 17, 2023

Despite the widespread presence of chiral cyclopentane motif, asymmetric synthesis cyclopentanes containing five stereocenters remains a formidable challenge. Here, we present an N-heterocyclic carbene (NHC)-catalyzed cascade reaction enal and oxindole-dienone, which allows access to spiroxindole featuring complete set centers on five-membered carbocycle. This strategy, characterized by formation multiple bonds centers, demonstrates broad substrate scope, exclusive diastereoselectivity, up 99:1 er.

Язык: Английский

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Construction of 3,4-Dihydroquinolone Derivatives through Pd-Catalyzed [4+2] Cycloaddition of Vinyl Benzoxazinanones with α-Alkylidene Succinimides

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(5), С. 3279 - 3291

Опубликована: Фев. 20, 2024

The construction of 3,4-dihydroquinolone derivatives has attracted a considerable amount attention due to their extensive applications in medicinal chemistry. In this study, we present the Pd-catalyzed [4+2] cycloaddition vinyl benzoxazinanones with α-alkylidene succinimides for efficient synthesis 3,4-dihydroquinolones. This approach presents numerous advantages, including ready availability starting materials, mild reaction conditions without use additional bases, and wide range substrates. particular, all desired products can be easily afforded high yields (≤99%) excellent diastereoselectivities (>20:1). practicality reliability strategy were demonstrated by successful scale-up subsequent straightforward synthetic transformations.

Язык: Английский

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Catalyst-controlled regiodivergence and stereodivergence in formal cross-[4+2] cycloadditions: The unique effect of bismuth(III)

Science Advances, Год журнала: 2025, Номер 11(13)

Опубликована: Март 26, 2025

The [4+2] cycloaddition is crucial for constructing six-membered rings in pharmaceuticals and natural products. Cross-[4+2] cycloadditions offer greater product diversity than traditional diene-dienophile reactions due to multiple possible pathways. However, precise control over regio- stereoselectivity various isomers remains a great challenge. This study reports catalyst-controlled regiodivergent formal cross-cycloadditions of acyclic dienes enones, significantly enhancing access diverse pyrazole-fused spirooxindoles. Chiral phosphoric acid (CPA) catalysis enables endoselective cycloadditions, while Bi(III) with CPA ligand yields [2+4] products high stereoselectivity. A Claisen rearrangement the adduct produces exo-selective product, further increasing stereochemical enabling synthesis six stereo-isomers from single substrate set. DFT calculations reveal that reverses regioselectivity by repositioning reactants pocket stabilizing enone oxygen’s negative charge. In addition, 3as demonstrates therapeutic potential against triple-negative breast cancer, an IC 50 8.5 μM MDA-MB-453 cells.

Язык: Английский

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