Transition‐Metal‐Mediated Fluoroalkylation of Carbon Electrophiles through Cross‐Electrophile Couplings DOI
Yun‐Cheng Luo, Xingang Zhang

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Comprehensive Summary Organofluorine compounds have attracted substantial interest in life and materials sciences due to the unique properties of fluorine atom(s) that often change physicochemical biological organic molecules. Transition‐metal‐mediated cross‐electrophile coupling between carbon electrophiles fluoroalkyl has emerged as a straightforward efficient route for synthesis wide range fluoroalkylated because its synthetic convenience without tedious organometallic reagents. Moreover, alkenes or alkynes‐involved three‐component couplings provide rapid effective access carbonfunctionalized alkanes alkenes. Herein, we comprehensively summarize transition‐metal‐mediated reductive fluoroalkylation diverse through historical perspective, including trifluoromethylation, difluoroalkylation, monofluoroalkylation, so on. Different transition metals (Cu, Ni, etc .) strategies are discussed, which nickel‐catalyzed reactions represent an attractive site‐selectively organofluorine compounds. Key Scientists As early 1965, McLoughlin Thrower finished first stoichiometric copper‐mediated aromatic iodides with iodides. However, excess elevated temperature were used this method. In 1969, Kobayashi Kumadaki reported studies on trifluoromethylation halides trifluoromethyl iodide. After more than four decades, Zhang group developed β ‐fluorinated alkylation (hetero)aryl secondary alkyl bromides 2015, difluoromethylation chlorides chlorodifluoromethane ClCF 2 H 2017. The also enantioselective alkyl‐arylation 3,3,3‐trifluoropropene tertiary 2018, MacMillan novel copper/photoredox dual catalytic system aryl ( S )‐(trifluoromethyl) dimesitylsulfonium triflate presence tris‐(trimethylsilyl) silanol. They nickel/photoredox catalyzed silane. During time, Wang monofluoroalkylation monofluoroalkyl halides. From 2021 2023, same further series trifluoroalkylation aryl, alkenyl, acyl nonfluorinated alkynes could be couplings. Chu fluoroalkyl‐acylation Later, they fluoroalkyl‐arylation unactivated tethering pendant chelating group. 2019, Chaładaj palladium‐catalyzed perfluoroalkyl‐arylation perfluoroalkyl

Language: Английский

Modular and Facile Access to Chiral α-Aryl Phosphates via Dual Nickel- and Photoredox-Catalyzed Reductive Cross-Coupling DOI

Hepan Wang,

Purui Zheng,

Xiaoqiang Wu

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(9), P. 3989 - 3997

Published: Feb. 22, 2022

Chiral phosphine-containing skeletons are important motifs in bioactive natural products, pharmaceuticals, chiral catalysts, and ligands. Herein, we report a general modular platform to access α-aryl phosphorus compounds via Ni/photoredox-catalyzed enantioconvergent reductive cross-coupling between α-bromophosphates aryl iodides. This dual catalytic regime exhibited high efficiency good functional group compacity. A wide variety of substrates bearing diverse set groups could be converted into phosphates excellent yields enantioselectivities. The utility the method was also demonstrated by development new phosphine ligand synthesis enzyme inhibitor derivatives. detailed mechanistic studies supported radical chain process revealed unique distinction compared with traditional cross-coupling.

Language: Английский

Citations

71
Oxidative addition of an alkyl halide to form a stable Cu(III) product DOI
Yongrui Luo, Yuli Li, Jian Wu

et al.

Science, Journal Year: 2023, Volume and Issue: 381(6662), P. 1072 - 1079

Published: Sept. 7, 2023

The step that cleaves the carbon-halogen bond in copper-catalyzed cross-coupling reactions remains ill defined because of multiple redox manifolds available to copper and instability high-valent product formed. We report oxidative addition α-haloacetonitrile ionic neutral copper(I) complexes form previously elusive but here fully characterized copper(III) complexes. stability these stems from strong Cu−CF 3 high barrier for C( CF )−C( CH 2 CN ) bond-forming reductive elimination. mechanistic studies we performed suggest proceeds by means two different pathways: an S N 2-type substitution complex a halogen-atom transfer complex. observed pronounced ligand acceleration addition, which correlates with couplings azoles, amines, or alkynes alkyl electrophiles.

Language: Английский

Citations

53
A Radical Strategy for the Alkylation of Amides with Alkyl Halides by Merging Boryl Radical-Mediated Halogen-Atom Transfer and Copper Catalysis DOI
Zhenhua Zhang, Lorenzo Poletti, Daniele Leonori

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22424 - 22430

Published: Aug. 1, 2024

Amide alkylation is a fundamental process in organic chemistry. However, the low nucleophilicity of amides means that divergent coupling with alkyl electrophiles often not achievable. To circumvent this reactivity challenge, individual amine synthesis followed by amidation standard agents generally required. Herein, we demonstrate radical solution to challenge using an amine–borane complex and copper catalysis under oxidative conditions. While borohydride reagents are used as reducing ionic chemistry, their conversion into amine-ligated boryl radicals diverts toward halogen-atom transfer. This enables halides corresponding for amide functionalization via catalysis. The applicable N-alkylation primary employing unactivated iodides bromides, it was also showcased late-state both amide- halide-containing drugs.

Language: Английский

Citations

18
An overview on copper in industrial chemistry: From ancient pigment to modern catalysis DOI
Mohammad Soleiman‐Beigi, Masoud Mohammadi,

Homa Kohzadi

et al.

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 529, P. 216438 - 216438

Published: Jan. 17, 2025

Language: Английский

Citations

2
Recent Advances in C(sp3)–C(sp3) Cross-Coupling Chemistry: A Dominant Performance of Nickel Catalysts DOI
Ramagonolla Kranthikumar

Organometallics, Journal Year: 2022, Volume and Issue: 41(6), P. 667 - 679

Published: March 4, 2022

The formation of a new C–C bond at sp3-hybridized centers is highly desirable, as it opens up unique, unexplored chemical space. revolutionary discoveries in this field meet the longstanding challenge forming stereocontrolled bonds and provide rapid access to C(sp3)-rich drug molecules. improved catalytic systems have enabled creative design challenging transformations. latest advancements nickel catalysis are particularly attractive shown excellent performance field. progress that has been made toward C(sp3)–C(sp3) (traditional cross-electrophile couplings) past decade highlighted review.

Language: Английский

Citations

64
Recent advances in the synthesis of 1,1-diarylalkanes by transition-metal catalysis DOI

Md. Belal,

Zheqi Li, Xiuqiang Lu

et al.

Science China Chemistry, Journal Year: 2021, Volume and Issue: 64(4), P. 513 - 533

Published: Jan. 12, 2021

Language: Английский

Citations

60
Copper‐Catalyzed Difluoromethylation of Alkyl Iodides Enabled by Aryl Radical Activation of Carbon–Iodine Bonds DOI
Aijie Cai, Wenhao Yan, Chao Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(52), P. 27070 - 27077

Published: Oct. 15, 2021

Abstract The engagement of unactivated alkyl halides in copper‐catalyzed cross‐coupling reactions has been historically challenging, due to their low reduction potential and the slow oxidative addition copper(I) catalysts. In this work, we report a novel strategy that leverages halogen abstraction ability aryl radicals, thereby engaging diverse range iodides Negishi‐type at room temperature. Specifically, radicals generated via copper catalysis efficiently initiate cleavage carbon–iodide bonds iodides. thus enter catalytic cycles couple with difluoromethyl zinc reagent, furnishing difluoromethane products. This unprecedented difluoromethylation approach applied late‐stage modification densely functionalized pharmaceutical agents natural

Language: Английский

Citations

56
A General Light‐Driven Organocatalytic Platform for the Activation of Inert Substrates DOI Creative Commons
Shuo Wu, Florian Schiel, Paolo Melchiorre

et al.

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

Published: June 16, 2023

Due to their strong covalent bonds and low reduction potentials, activating inert substrates is challenging. Recent advances in photoredox catalysis offered a number of solutions, each which useful for specific bonds. Developing general catalytic platform that can consistently target broad range would be synthetically useful. Herein, we report readily available indole thiolate organocatalyst that, upon excitation with 405 nm light, acquires strongly reducing power. This excited-state reactivity served activate, by single-electron reduction, C-F, C-Cl, C-O both aromatic aliphatic substrates. was versatile enough promote the generally recalcitrant electron-rich (Ered <-3.0 V vs SCE), including arenes afforded 1,4-cyclohexadienes. The protocol also borylation phosphorylation high functional group tolerance. Mechanistic studies identified an anion as responsible highly reactivity.

Language: Английский

Citations

40
Copper-catalyzed Sonogashira reactions: advances and perspectives since 2014 DOI Creative Commons

Koduvarathodi Vadakkethil Arundhathi,

Palemkunnummal Vaishnavi,

Thaipparambil Aneeja

et al.

RSC Advances, Journal Year: 2023, Volume and Issue: 13(7), P. 4823 - 4834

Published: Jan. 1, 2023

This review summarizes the recent advances and perspectives in copper catalyzed Sonogashira reaction covering both homogeneous heterogeneous systems.

Language: Английский

Citations

36
Catalytically Relevant Organocopper(III) Complexes Formed through Aryl-Radical-Enabled Oxidative Addition DOI
Wenhao Yan, Andrew T. Poore, Lingfeng Yin

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15176 - 15185

Published: May 21, 2024

Stepwise oxidative addition of copper(I) complexes to form copper(III) species via single electron transfer (SET) events has been widely proposed in copper catalysis. However, direct observation and detailed investigation these fundamental steps remain elusive owing largely the typically slow rate instability species. We report herein a novel aryl-radical-enabled stepwise pathway that allows for formation well-defined alkyl–CuIII from CuI complexes. The process is enabled by SET an aryl diazonium salt CuII radical. Subsequent iodine abstraction alkyl iodide radical affords radical, which then reacts with complex. structure resultant [(bpy)CuIII(CF3)2(alkyl)] characterized NMR spectroscopy X-ray crystallography. Competition experiments have revealed at different iodides undergo consistent carbon-centered radicals. intermediate formed during identified as four-coordinate complex, [CuII(CH3CN)2(CF3)2], through electronic paramagnetic resonance (EPR) studies. catalytic relevance high-valent organo-CuIII demonstrated C–C bond-forming reductive elimination reactivity. Finally, localized orbital bonding analysis formal CuIII indicates inverted ligand fields σ(Cu–CH2) bonds. These results demonstrate catalysis provide general strategy investigate

Language: Английский

Citations

13