Ruthenium-Catalyzed Chemoselective N–H Bond Insertion Reactions of 2-Pyridones/7-Azaindoles with Sulfoxonium Ylides

Organic Letters, Год журнала: 2021, Номер 23(3), С. 1038 - 1043

Опубликована: Янв. 21, 2021

A ruthenium-catalyzed highly chemoselective N-alkylation of 2-pyridones has been developed, affording N-alkylated 2-pyridone derivatives in good yields and excellent N-selectivity. The key to achieve this unprecedented N–H rather than O–H insertion reaction is the use CpRu(PPh3)2Cl as catalyst sulfoxonium ylides alkylation reagents. Moreover, protocol also amenable 7-azaindoles by slightly varying conditions. Furthermore, sulfonium are suitable reagents, providing selectivity.

Язык: Английский

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Divergent Synthesis of Tetrasubstituted Phenols via [3 + 3] Cycloaddition Reaction of Vinyl Sulfoxonnium Ylides with Cyclopropenones

Organic Letters, Год журнала: 2023, Номер 25(23), С. 4286 - 4291

Опубликована: Июнь 2, 2023

Two categories of tetrasubstituted phenols were prepared via the cycloaddition reaction vinyl sulfoxonnium ylides with cyclopropenones in a switchable manner. Copper carbenoid was proposed as active intermediate process 2,3,4,5-tetrasubstituted formation, while 2,3,5,6-tetrasubstituted generated direct [3 + 3] annulation under metal-free conditions. Further synthetic applications also demonstrated.

Язык: Английский

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Metal-free cascade O–H double insertion between I^(III)/S^(VI)-ylides, carboxylic acids, and alcohols: modular access to unsymmetrical α,α-O,O-substituted ketones

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(11), С. 3234 - 3241

Опубликована: Янв. 1, 2024

Herein, we present a cascade O–H double insertion reaction between I (III) /S (VI) -ylides, carboxylic acids, and alcohols under metal-free conditions, enabling the modular synthesis of unsymmetrical α,α- O , -substituted ketones.

Язык: Английский

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Palladium-Catalyzed Direct and Specific C-7 Acylation of Indolines with 1,2-Diketones

Organic Letters, Год журнала: 2021, Номер 23(2), С. 410 - 415

Опубликована: Янв. 5, 2021

The indole scaffold is a ubiquitous and useful substructure, extensive investigations have been conducted to construct the framework and/or realize modification. Nevertheless, direct selective functionalization on benzenoid core must overcome high activity of C-3 position still remains highly challenging. Herein, palladium-catalyzed specific C-7 acylation indolines in presence an easily removed directing group was developed. This strategy usually considered as practical for preparation acylated indoles because indoline can be converted under oxidation conditions. In particular, our greatly improved alkacylation yield which only unsatisfactory could achieved previous studies. Furthermore, reaction scaled up gram level standard conditions with much lower palladium loading (1 mol %).

Язык: Английский

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Enantioselective Indole Insertion Reactions of α-Carbonyl Sulfoxonium Ylides

Organic Letters, Год журнала: 2021, Номер 23(24), С. 9446 - 9450

Опубликована: Дек. 2, 2021

The first example of organocatalytic enantioselective C–H insertion reactions indoles and sulfoxonium ylides is reported. Under the influence phosphoric acid catalysis, levels enantiocontrol in range 20–93% ee moderate yields (up to 50%) were achieved for 29 examples formal free α-carbonyl ylides. No nitrogen protection on indole necessary.

Язык: Английский

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α-Carbonyl sulfoxonium ylides in transition metal-catalyzed C–H activation: a safe carbene precursor and a weak directing group

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 21(5), С. 879 - 909

Опубликована: Дек. 6, 2022

Transition metal-catalyzed cross-coupling of sp2 C-H bonds with diazo compounds via carbene migratory insertion represents an efficient strategy for the construction C-C and C-heteroatom in organic synthesis. Despite popularity as coupling partners activation, they pose serious safety stability issues due to potential exothermic reactions linked release N2 gas. However, compared compounds, sulfoxonium ylides are generally crystalline solids, more stable, widely used industrial scales, easier/safer prepare. Therefore, recent years have witnessed upsurge employing α-carbonyl alternative surrogate transition activation. Unlike contain inherent serve a partner well weak directing group. This review will summarize progress made both categories reactions.

Язык: Английский

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Cascade C–H Activation/Annulation of Sulfoxonium Ylides with Vinyl Cyclopropanes: Access to Cyclopropane-Fused α-Tetralones

Organic Letters, Год журнала: 2023, Номер 25(19), С. 3352 - 3357

Опубликована: Май 4, 2023

Rh-catalyzed weak and traceless directing-group-assisted cascade C–H activation annulation of sulfoxonium ylides with vinyl cyclopropanes as a coupling partner have been accomplished to furnish functionalized cyclopropane-fused tetralones at moderate temperature. The C–C bond formation, cyclopropanation, functional group tolerance, late-stage diversifications drug molecules, scale-up are the important practical features.

Язык: Английский

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Recent advance: Sulfur ylides in organic synthesis

Journal of Heterocyclic Chemistry, Год журнала: 2023, Номер 61(1), С. 29 - 70

Опубликована: Окт. 26, 2023

Abstract Sulfur ylides are versatile structures that display various characteristics and participate in a myriad of reactions to produce simple, effective, sometimes stereoselective toward synthesizing sulfur‐containing compounds. Nonetheless, their fulfillment tremendous developments have been made this field the past few decades. In comprehensive review, luminosity is illuminated on application sulfur involved domino, cascade annulation reactions, carbene trapping reagents with chameleonic reactivity. numerous decennary, chemists used solvent‐dependent, rhodium catalyzed, dealkylative intercepted, photochemical reaction, halotrifluoromethylation, benzannulation, amidation name such as Mizoroki–Heck, Suzuki–Miyaura, Sommelet–Hauser rearrangements. Moreover, other prime applications include metal catalysis, epoxidation carbonyl compounds, acylmethylation, cyclomerization, oxidation, insertion reactions. Additionally, some extremely useful play major role synthesis medicinally active heterocycles structural motifs. This review article discusses all these proposed mechanisms, current scenario, at length. tutorial concludes by providing future outlook investigation into compounds synthesized using it great potential be industries, laboratories, pharmaceutical companies, drug production, clinical use, medicinal chemistry, agrochemical purposes.

Язык: Английский

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Divergent Construction of α,α-Difunctionalized Ketones via [1,2]-Sigmatropic Rearrangement/Alkylation-Hydroxylation/Dialkylation of I^(III)/S^(VI) Ylides

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

The rare [1,2]-sigmatropic rearrangement of sulfoxonium-iodonium hybrid ylides is described, which enables the efficient sulfoxidation/sulfonylation-alkylation I(III)/S(VI) with 1,3-dicarbonyls. By slight modification reaction conditions, controllable alkylation-hydroxylation and dialkylation were achieved. This strategy affords a diverse array α,α-difunctionalized ketones in moderate to good yields, demonstrating broad substrate scope. These findings provide an important advancement sulfoxonium highlight divergent reactivity ylides.

Язык: Английский

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Divergent Synthesis of Dihydrofuran and Dienol Scaffolds via Pd-Catalyzed Decarboxylative Carbene Cross-Coupling

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 24, 2025

Herein, we report a novel ligand-switchable Pd-catalyzed carbene coupling reaction employing vinylethylene carbonates and sulfoxonium ylides. By proper choice of ligands, the chemoselectivity process could be efficiently regulated, allowing for availability dihydrofuran or dienol scaffolds. This method features mild conditions, broad scope, remarkable synthetic utility. Compound 6f can effectively stimulate secretion GLP-1, providing promising insight into development small-molecule agonists GLP-1 receptor.

Язык: Английский

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