Carbofluorination of Alkenes with gem-Difluorinated Cyclopropanes as Bifunctional Reagents Enabled by Well-Define Rhodium Catalysts DOI Creative Commons
Yaxin Zeng, Zhong‐Tao Jiang,

Yulei Zhu

et al.

Published: Aug. 21, 2023

Herein, we report a Rh-catalyzed carbofluorination of alkenes using gem-difluorinated cyclopropanes as bifunctional reagents. The developed method tolerates wide range alkenes, providing access to secondary, tertiary fluorides and gem-difluorides with 100% atom-economy under mild conditions. resulting can be further transformed yield C−C, C−N, C−O bifunctionalization products. Cationic dicarbonyl rhodium tetrafluoroborate has been identified the only highly efficient catalyst in this reaction. Preliminary mechanistic studies reveal that addition fluorine atom is mediated by ion, which acts anion shuttle.

Language: Английский

Recent Advances in Transition-Metal-Catalyzed Cross-Coupling Reactions of gem-Difluorinated Cyclopropanes DOI
Ying Xia,

Yulei Zhu,

Yaxin Zeng

et al.

Synlett, Journal Year: 2022, Volume and Issue: 34(01), P. 1 - 13

Published: July 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

Language: Английский

Citations

39
Rhodium‐Catalyzed Regio‐ and Diastereoselective [3+2] Cycloaddition of gem‐Difluorinated Cyclopropanes with Internal Olefins DOI
Yaxin Zeng, Ying Xia

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: June 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.

Language: Английский

Citations

33
Stereoselective Photoredox Catalyzed (3+3) Dipolar Cycloaddition of Nitrone with Aryl Cyclopropane DOI
Yao Xu, Haixiang Gao,

Chengkai Pan

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 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.

Language: Английский

Citations

25
Visible light-mediated ring opening and cyclization of aryl cyclopropanes: efficient synthesis of pyrrolo[1,2-a]quinoxalin-4(5H)-ones with antineoplastic activity DOI
Jiabin Shen, Yong Yang, Chao Chen

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(6), P. 1758 - 1764

Published: Jan. 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.

Language: Английский

Citations

13
Selectivity in Rh-catalysis with gem-difluorinated cyclopropanes DOI
Yaxin Zeng, Zhong‐Tao Jiang, Ying Xia

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(28), P. 3764 - 3773

Published: Jan. 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.

Language: Английский

Citations

12
Gold(I)-Catalyzed [2 + 2] and [3 + 2] Cycloadditions of 1,1-Difluoroallenes with Aldehydes: Switchable Syntheses of Fluorinated Oxetanes and Furans DOI

Daisuke Miyazaki,

Kazuko Kudo,

Yusuke Fujiki

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

Citations

1
Difluoroalkylative carbonylation of alkenes to access carbonyl difluoro-containing heterocycles: convenient synthesis of gemigliptin DOI Creative Commons
Zhipeng Bao, Youcan Zhang,

Le‐Cheng Wang

et al.

Science China Chemistry, Journal Year: 2022, Volume and Issue: 66(1), P. 139 - 146

Published: Dec. 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.

Language: Английский

Citations

34
Donor‐Acceptor Cyclopropanes: Activation Enabled by a Single, Vinylogous Acceptor DOI Creative Commons
Nils L. Ahlburg,

Oliver Hergert,

Peter G. Jones

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(1)

Published: Nov. 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.

Language: Английский

Citations

29
Construction and transformations of 2,2-difluoro-2,3-dihydrofurans from enaminones and diflurocarbene DOI

Heyun Sheng,

Zhiwei Chen, Xue Li

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(11), P. 3000 - 3005

Published: Jan. 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.

Language: Английский

Citations

27
Synthesis of Heterocycles from Donor-Acceptor Cyclopropanes: A Five-Year Recap DOI
Ani Deepthi,

C.B. Meenakshy,

Maneesh Mohan

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 55(23), P. 3875 - 3894

Published: May 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

Language: Английский

Citations

14