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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Convenient synthesis of chromene-fused spirocyclopentane-1,2-dioxindoles via base promoted annulation reaction

Tetrahedron Letters, Год журнала: 2025, Номер 156, С. 155455 - 155455

Опубликована: Янв. 8, 2025

Язык: Английский

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Phosphine‐Catalyzed (3 + 2) Annulation of δ‐Hydroxyl Allenylic Alcohols with Pyrazolinone‐Derived Ketimines

ChemistrySelect, Год журнала: 2025, Номер 10(3)

Опубликована: Янв. 1, 2025

Abstract The phosphine‐catalyzed (3 + 2) annulation reaction of δ ‐hydroxyl‐substituted allenylic alcohols with pyrazolinone‐derived ketimines has been developed, giving a variety spiro dihydropyrrole‐dihydropyrazolone derivatives in high yields good diastereoselectivities. Various unsaturated and diverse worked well under mild conditions, 31 examples were provided up to 97% yield >20:1 diastereoselectivity. scale‐up further transformations the product successfully acheived, three derivation experiments showed feasibility product. These results revealed that current could be useful tool for synthesis derivatives. In addition, we also investigated asymmetric version this ketimines, 86% ee chiral was obtained use bifunctional phosphine catalyst.

Язык: Английский

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Molecular diversity of the reactions of MBH carbonates of isatins and various nucleophiles

Beilstein Journal of Organic Chemistry, Год журнала: 2025, Номер 21, С. 286 - 295

Опубликована: Фев. 6, 2025

In this paper, the nucleophilic substitution reactions of various N- and P-containing nucleophiles to MBH carbonates isatins were investigated. Diverse functionalized 3-substituted oxindole derivatives successfully prepared in satisfactory yields with high diastereoselectivity. addition, base-promoted dimerization isatin afforded ethylene-bridged bis(3-methylene)oxindole nearly 4:1 diastereomeric ratios. The relative configurations polycyclic compounds clearly elucidated by determination several single crystal structures.

Язык: Английский

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N-Heterocyclic Carbene-Catalyzed [4＋2] Cycloaddition of Salicylaldehydes with Pyrazole-4,5-diones for the Synthesis of Spiroketal-Pyrazolones

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(1), С. 267 - 267

Опубликована: Янв. 1, 2025

Язык: Английский

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Asymmetric Construction of Bis‐Spirocyclic Pyrazolones Bearing Vicinal Quaternary Carbon Centers

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(25)

Опубликована: Апрель 8, 2024

Abstract A catalytic asymmetric (3+2) cyclization of pyrazolone‐based MBH adducts with alkylidenyl isoxazolones was presented by using DMAP‐derived chiral catalyst, affording bis‐spirocyclic pyrazolones bearing vicinal all‐carbon quaternary stereocenters within an imbedded cyclopentene ring scaffold in good yields excellent stereoselectivities under mild conditions.

Язык: Английский

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An Efficient Route to Access Spirooxindole–Pyrazolone-Fused Cyclopentenes by a Diastereoselective [3+2] Annulation

Synlett, Год журнала: 2023, Номер 34(14), С. 1732 - 1738

Опубликована: Янв. 16, 2023

Abstract A DMAP-catalyzed, highly diastereoselective, [3+2] cycloaddition of pyrazolone-derived Morita–Baylis–Hillman carbonates to 3-methyleneoxindoles has been developed. variety structurally diverse and complex spiropyrazolone-fused oxindoles bearing three contiguous chiral centers have synthesized in high yields (up 98%) with excellent diastereoselectivities 99:1). Moreover, the synthetic potential this protocol demonstrated by performing a Suzuki coupling reaction.

Язык: Английский

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N-Heterocyclic Carbene (NHC)-Catalyzed [3+2] Cycloaddition to Highly Diastereoselective Synthesis of Spirooxindole Dihydrofuran Fused Pyrazolone Compounds

Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(4), С. 1301 - 1301

Опубликована: Янв. 1, 2024

An efficient N-heterocyclic carbene (NHC)-catalyzed [3＋2] cycloaddition of isatin-derived enal and pyrazole-4,5diones to directly synthesis spirooxindole dihydrofuran fused pyrazolone compounds containing two vicinal spirocenters was disclosed.This approach qualified with broad substrate scope, achieving moderate excellent yield (41%～99%) general diastereoselective (2∶1～＞20∶1 dr).Furthermore, the reaction has advantages mild conditions easy operation, gram scale can also proceed smoothly.This study provides a new synthetic methodology for construction multi-functionalized compounds.

Язык: Английский

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Asymmetric Synthesis of Spirooxindole Lactones by Ammonium-tethered Chiral Organocatalysts catalyzed Michael Addition/Cyclization of 3- hydroxyoxindoles with α,β-unsaturated Aldehydes

Current Catalysis, Год журнала: 2023, Номер 12(1), С. 34 - 42

Опубликована: Апрель 1, 2023

Abstract: The ammonium-tethered pyrrolidine-based organocatalyst catalyzed asymmetric Michael addition/cyclization reaction of α,β-unsaturated aldehydes with 3-hydroxyoxindole in aqueous media was developed, giving the spirooxidole lactones high yields enantioselectivities. Background: 3-hydroxyoxindoles α,β- unsaturated is an important method for synthesis chiral spirooxindole derivatives, which are found a wide range biologically active natural products and pharmaceutical agents. Objective: Organocatalyzed reactions one most powerful effective approaches construction complex molecules from relatively simple starting materials. However, major problem associated these organocatalytic system that catalyst loading organic solvents required. In present work, our objective to develop water-compatible aimed at lowering being system. Methods: typical experiment, To solution 2a (0.008 mmol) PhCO2H (0.096 0.5 mL mixture solvent iPrOH/H2O (1:3) added aldehyde (0.4 (0.8 mmol). proceeded room temperature 16 hours, then extracted 10 dichloromethane give cyclized hemiacetal, subjected direct oxidation pyridinium chlorochromate (PCC, 1.2 hours desired lactones. Results: successfully gave excellent (81-95%) moderate enantioselectivities (up 99% ee). diastereoselectivities were poor ranging 1:1.1 1:2.3. Conclusion: using has been developed. performed low (2 mol%) provided (ee: up 99%).

Язык: Английский

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Phosphine‐Catalyzed (3+2) Annulation of Morita‐Baylis‐Hillman Carbonates with Pyrazolinone‐Derived Ketimines: Synthesis of Spirodihydropyrrole‐Dihydropyrazolones

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(46)

Опубликована: Окт. 11, 2023

Abstract A phosphine‐catalyzed (3+2) annulation of Morita‐Baylis‐Hillman carbonates with pyrazolinone‐derived ketimines has been achieved to give various spirodihydropyrrole‐dihydropyrazolones in moderate high yields good diastereoselectivities. The reaction tolerated diverse MBH and ketimines. Both scale‐up further transformation the product were successfully performed. In addition, up 98 % ee chiral was obtained use bifunctional phosphine.

Язык: Английский

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