Recent Advances in Transition-Metal-Catalyzed Cross-Coupling Reactions of gem-Difluorinated Cyclopropanes

Synlett, Год журнала: 2022, Номер 34(01), С. 1 - 13

Опубликована: Июль 28, 2022

Abstract As a special class of cyclopropanes, gem-difluorinated cyclopropanes have many fascinating properties as result the gem-difluoro substitution; thus, their reactions received much attention from synthetic chemistry community. Recently, gradually emerged type novel and unique fluorinated allylic synthon in cross-coupling for synthesis monofluoroalkenes. Herein, we briefly summarize recent advances transition-metal-catalyzed cyclopropanes. 1 Introduction 2 Palladium-Catalyzed Reactions with Linear Selectivity 3 Branched 4 Other Metal-Catalyzed 5 Conclusions

Язык: Английский

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Rhodium‐Catalyzed Regio‐ and Diastereoselective [3+2] Cycloaddition of gem‐Difluorinated Cyclopropanes with Internal Olefins

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(32)

Опубликована: Июнь 20, 2023

Direct synthesis of gem-difluorinated carbocyclic molecules represents a longstanding challenge in organic chemistry. Herein, Rh-catalyzed [3+2] cycloaddition reaction between readily available cyclopropanes (gem-DFCPs) and internal olefins has been developed, enabling the efficient cyclopentanes with good functional group compatibility, excellent regioselectivity diastereoselectivity. The resulting products can undergo downstream transformations to access various mono-fluorinated cyclopentenes cyclopentanes. This demonstrates use gem-DFCPs as type "CF2 " C3 synthon for under transition metal catalysis, which provides potential strategy synthesizing other molecules.

Язык: Английский

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Stereoselective Photoredox Catalyzed (3+3) Dipolar Cycloaddition of Nitrone with Aryl Cyclopropane

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(44)

Опубликована: Сен. 13, 2023

Abstract By resorting to the principle of remote activation, we herein demonstrate first photoredox catalyzed (3+3) dipolar cycloaddition nitrones with aryl cyclopropanes. Key fidelity reaction resides in a facile manner substrate activation by single‐electron transfer (SET) oxidation catalysis, and takes place through stepwise cascade encompassing three‐electron‐type nucleophilic substitution triggered cyclopropane ring‐opening diastereoselective 6‐endo‐ trig radical cyclization manifold. The proceeds under mild conditions excellent regio‐ stereoselectivity, nicely complementing well‐developed Lewis acid donor‐acceptor Other merits protocol include wide scope cyclopropanes diversified patterns good functional‐group compatibility. A mechanism involving an cation promoted mode was also proposed supported mechanistic experiments.

Язык: Английский

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Visible light-mediated ring opening and cyclization of aryl cyclopropanes: efficient synthesis of pyrrolo[1,2-a]quinoxalin-4(5H)-ones with antineoplastic activity

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(6), С. 1758 - 1764

Опубликована: Янв. 1, 2024

This study describes an efficient and green approach for the synthesis of potentially bioactive pyrrolo[1,2- a ]quinoxalin-4(5 H )-ones with appreciable functional group tolerance wide substrate scope.

Язык: Английский

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Selectivity in Rh-catalysis with gem-difluorinated cyclopropanes

Chemical Communications, Год журнала: 2024, Номер 60(28), С. 3764 - 3773

Опубликована: Янв. 1, 2024

This feature article summarizes our efforts towards developing Rh-catalyzed reactions of gem -difluorinated cyclopropanes, briefly discussing the design, selectivity, mechanisms and future research prospects.

Язык: Английский

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Gold(I)-Catalyzed [2 + 2] and [3 + 2] Cycloadditions of 1,1-Difluoroallenes with Aldehydes: Switchable Syntheses of Fluorinated Oxetanes and Furans

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 18, 2025

1,1-Difluoroallenes underwent regioselective [2 + 2] and [3 cycloadditions with aldehydes using Au(I) catalysts. An AuCl catalyst enabled an α,β-selective cycloaddition of 1,1-difluoroallenes, yielding (E)-3-alkylidene-2,2-difluorooxetanes. Conversely, AuCl(IPr)-AgSbF6 facilitated α,γ-selective cycloaddition, followed by dehydrofluorination to produce aromatized 2-fluorofurans. DFT calculations (B3LYP level) suggested that the former reaction proceeded through Au(III)-containing metallacycles, while latter involved cyclic carbenoids.

Язык: Английский

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Difluoroalkylative carbonylation of alkenes to access carbonyl difluoro-containing heterocycles: convenient synthesis of gemigliptin

Science China Chemistry, Год журнала: 2022, Номер 66(1), С. 139 - 146

Опубликована: Дек. 12, 2022

Abstract Fluorinated heterocycles play a vital role in pharmaceutical and agrochemical industries. Hence, rapid efficient construction of fluorinated remains highly demanded. Herein, difluoroalkylative carbonylative cyclization unactivated alkenes ethylene gas enabled by palladium catalysis has been developed for the first time toward synthesis α-carbonyl difluoro-modified glutarimides. This procedure can also be applied to GeMigliptin which is medicine approved treatment type 2 diabetes mellitus.

Язык: Английский

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Donor‐Acceptor Cyclopropanes: Activation Enabled by a Single, Vinylogous Acceptor

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(1)

Опубликована: Ноя. 2, 2022

A novel class of highly activated donor-acceptor cyclopropanes bearing only a single, vinylogous acceptor is presented. These strained moieties readily undergo cycloadditions with aldehydes, ketones, thioketones, nitriles, naphth-2-ols and various other substrates to yield the corresponding carbo- heterocycles. Diastereocontrol can be achieved through choice catalyst (Brønsted or Lewis acid). The formation tetrahydrofurans was shown enantiospecific when chiral are employed. series mechanistic kinetic experiments conducted elucidate plausible catalytic cycle rationalize stereochemical outcome.

Язык: Английский

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Construction and transformations of 2,2-difluoro-2,3-dihydrofurans from enaminones and diflurocarbene

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(11), С. 3000 - 3005

Опубликована: Янв. 1, 2022

A simple and efficient construction of 2-difluoro-2,3-dihydrofurans is reported, which features metal-free additive-free conditions, high functional group tolerance readily accessible starting materials.

Язык: Английский

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Synthesis of Heterocycles from Donor-Acceptor Cyclopropanes: A Five-Year Recap

Synthesis, Год журнала: 2023, Номер 55(23), С. 3875 - 3894

Опубликована: Май 22, 2023

Abstract This review discusses the utility of donor-acceptor cyclopropanes (DACs) for construction heterocycles. In addition to (3+2), (3+3), and (4+3) cycloaddition pathways, nucleophilic ring-opening reactions, intramolecular transformations, cycloisomerizations in presence suitable catalysts pave way generation heterocycles from DACs. The mild reactions conditions employed variety starting materials that can be used as reaction partners make DAC route heterocycle synthesis attractive. literature covered this is period 2018 2023. 1 Introduction 2 Synthesis Nitrogen Heterocycles 2.1 By Annulations with Anthranils Azadienes 2.2 Nucleophilic Attack Anilines Hydrazones 2.3 Reaction Ureas Thioureas 2.4 Annulation Reactions Using an Azomethine Imine 2.5 Other 2.6 Transformations 3 Oxygen 3.1 Intramolecular 3.2 Intermolecular 4 Sulfur Selenium 4.1 Thiocarbonyl Substrates 4.2 Thio- Selenocyanates Thiosulfonate Salts 5 N–S N–O 6 Conclusions

Язык: Английский

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