Radical-Polar Crossover Enabled Triple Cleavage of CF₂Br₂: A Multicomponent Tandem Cyclization to 3-Fluoropyrazoles

Organic Letters, Год журнала: 2023, Номер 25(32), С. 6062 - 6066

Опубликована: Авг. 8, 2023

The elaboration of step-economy and catalytic approaches for accessing diverse fluorinated heterocyclics is highly desirable. Described herein a radical-polar crossover enabled three-component cyclization to polysubstituted fluoropyrazoles by using CF2Br2 as novel C1F1 synthon. Mechanistic experiments revealed that the in situ generation reactive intermediate gem-difluorovinylimine ion key this transformation. This protocol unlocks reactivity adds significant synthetic values fluorine chemistry.

Язык: Английский

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Iodopentafluorosulfanylation of [1.1.1]propellane and further functionalizations

Science China Chemistry, Год журнала: 2023, Номер 66(10), С. 2871 - 2877

Опубликована: Авг. 24, 2023

Язык: Английский

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Switching from 2-pyridination to difluoromethylation: ligand-enabled nickel-catalyzed reductive difluoromethylation of aryl iodides with difluoromethyl 2-pyridyl sulfone

Science China Chemistry, Год журнала: 2023, Номер 66(10), С. 2785 - 2790

Опубликована: Сен. 18, 2023

Язык: Английский

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Synthesis and clinical application of representative small-molecule dipeptidyl Peptidase-4 (DPP-4) inhibitors for the treatment of type 2 diabetes mellitus (T2DM)

European Journal of Medicinal Chemistry, Год журнала: 2024, Номер 272, С. 116464 - 116464

Опубликована: Май 1, 2024

Язык: Английский

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Palladium-catalyzed oxidative double alkoxycarbonylation of ethylene toward succinic acid derivatives

Green Carbon, Год журнала: 2024, Номер 2(2), С. 205 - 208

Опубликована: Апрель 2, 2024

Employing biodegradable plastics is one of the choices to solve white pollution issues. PBS (polybutylene succinate), as a plastic with good stability and heat resistance, produced by polymerization succinic acid butylene glycol. However, inadequate supply direct upstream material restricts development this industry. In work, we provide carbonylative strategy construct derivatives from carbon monoxide, ethylene alcohols. The reaction catalyzed palladium catalyst under oxidative conditions.

Язык: Английский

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Carbonylative Transformations Using a DMAP-Based Pd-Catalyst through Ex Situ CO Generation

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(21), С. 15218 - 15236

Опубликована: Окт. 24, 2023

A phosphine-free, efficient protocol for aminocarbonylation and carbonylative Suzuki-Miyaura coupling has been developed using a novel palladium complex, [PdII(DMAP)2(OAc)2]. The complex was successfully synthesized stoichiometric reaction between PdII(OAc)2 DMAP in acetone at room temperature characterized single-crystal X-ray analysis. Only 5 mol % catalyst loading sufficient effective transformations. "Chloroform-COware" chemistry utilized safe facile insertion of the carbonyl unit chloroform as an inexpensive CO source two-chamber setup. Various value-added pharmaceutically relevant compounds such CX-516, CX-546, farampator were technique. Furthermore, commercially designed COware engineered to COware-RB setup sequential one-pot synthesis indenoisoquinolines (topoisomerase I inhibitors).

Язык: Английский

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Single-Electron-Transfer-Mediated Carbonylation Reactions

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Март 5, 2025

ConspectusTransition-metal-catalyzed carbonylation coupling methods have been accepted as an essential tool for producing carbonylated products over the past few decades. Despite its long-standing history and widespread industrial applications, several challenges remain in chemistry. These include reliance on precious metal catalysts, need of high-energy radiation, difficulties unactivated chemical bonds, etc. As alternative to classic two-electron transfer process, single-electron-transfer (SET)-mediated has emerged a powerful achieve elusive transformations. Over years, commonly available functional handles, such alkenes alkyl halides, via single-electron pathway valuable area research.Our team dedicated developing new reactions using bulk chemicals construct high-value products. broad synthetic motivating us explore SET-mediated transformations two key classes chemicals: alkanes halides. Specifically, our work centered main approaches: (1) Single-electron reduction C(sp3)-X bonds: this strategy leverages activate promoting formation carbon radicals, which turn promotes subsequent addition metals or CO. However, significant challenge lies highly negative potential certain substrates [Ered < -2 V compared saturated calomel electrode (SCE) iodides]. these challenges, intrinsic reducibility CO reactivity various carbonyl-metal intermediates facilitate smooth reaction progress. (2) oxidative C(sp3)-H emphasizes efficiency, high atomic utilization, minimal waste by bypassing traditional preactivation methods. Using 3d we successfully performed aminocarbonylation alkoxycarbonylation wide range bonds (such those aliphatic alkanes, ethers, amines, etc.). The above approaches also enabled radical relay alkenes, allowing precise control pathways. Such improves both efficiency selectivity. advancements transition photoredox catalysis resulting oxyalkylative carbonylation, aminoalkylative fluoroalkylative double rearrangement carbonylation.SET-mediated significantly enhances sustainability scalability process reducing catalysts enabling milder conditions. Additionally, carefully controlling intermediates, fine-tuned produce with This flexibility expands applications chemistry processes. Finally, place particular emphasis application drug discovery, where they serve handles late-stage modification bioactive molecules. applicability enriches toolbox synthesis, efficient functionalization complex versatile approach accelerate discovery novel therapeutic agents, making it critical modern medicinal

Язык: Английский

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Carbonylative five-component synthesis of amides and esters with α-quaternary carbon center

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111150 - 111150

Опубликована: Март 1, 2025

Язык: Английский

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Palladium-Catalyzed Four-Component Radical Cascade Carbonylation Access to 2,3-Disubstituted Benzofuran Derivatives

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 24, 2024

Multicomponent radical tandem reactions have emerged as a crucial technique for synthesizing complex molecules in organic chemistry. In this study, we report palladium-catalyzed four-component difluoroalkylative carbonylation of enynes and ethyl difluoroiodoacetate. This transformation proceeds through multistep sequential reaction that introduces reactive difluoro carbonyl groups while constructing the benzofuran skeleton. Moreover, variety valuable 2,3-disubstituted derivatives were obtained respectable yields with excellent functional group compatibility.

Язык: Английский

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Palladium-catalyzed carbonylation of activated alkyl halides via radical intermediates

Industrial Chemistry and Materials, Год журнала: 2023, Номер 2(2), С. 276 - 283

Опубликована: Авг. 16, 2023

In this review, we summarize and discuss recent achievements in palladium-catalyzed carbonylative reactions of activated alkyl halides. Aliphatic carboxylic acid derivates were prepared effectively with various nucleophiles.

Язык: Английский

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