Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(17), P. 4722 - 4729
Published: Jan. 1, 2024
The concurrent reduction of α-trifluoromethyl alkyl bromides and the cross-coupling THF with heterocycles in one pot have been realized through synergetic action a halogen bond Ni catalysis.
Language: Английский
Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown
Published: Nov. 26, 2024
Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp
Language: Английский
Citations
18
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)
Published: April 15, 2024
With halogen-atom transfer as an effective tool, a novel catalytic enantioselective protocol to generate chiral trifluoromethylated alkynes has been established by cooperative photoredox and nickel catalysis system, providing straightforward modular route access this type of product in good yields enantioselectivities. The process is essential for the reaction strategy offers another promising way utilize alkyl halides with highly negative reduction potentials. It firstly expands nickel-catalyzed asymmetric reductive cross-couplings organohalides from traditional single-electron transfer.
Language: Английский
Citations
11
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
Citations
9
Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)
Published: Jan. 11, 2025
The difluoromethyl group is a crucial fluorinated moiety with distinctive biological properties, and the synthesis of chiral CF₂H-containing analogs has been recognized as powerful strategy in drug design. To date, most established method for accessing enantioenriched compounds involves enantioselective functionalization nucleophilic electrophilic CF₂H synthons. However, this approach limited by lower reactivity reduced enantioselectivity. Leveraging unique fluorine effect, we design synthesize radical synthon incorporating isoindolinone into alkyl halides asymmetric transformation. Here, report an efficient construction carbon stereocenters featuring via nickel-catalyzed Negishi cross-coupling. This demonstrates mild reaction conditions excellent Given that optically pure difluoromethylated amines isoindolinones are key structural motifs bioactive compounds, offers practical solution drug-like molecules. moiety, screening. authors
Language: Английский
Citations
1
Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(14), P. 1997 - 2011
Published: July 4, 2024
ConspectusIn recent years, nickel-catalyzed asymmetric coupling reactions have emerged as efficient methods for constructing chiral C(sp
Language: Английский
Citations
8
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: March 28, 2024
Abstract Transition metal-catalyzed enantioconvergent cross-coupling of an alkyl precursor presents a promising method for producing enantioenriched C(sp 3 ) molecules. Because alcohol is ubiquitous and abundant family feedstock in nature, the direct reductive coupling aryl halide enables efficient access to valuable compounds. Although several strategies have been developed overcome high bond dissociation energy C − O bond, asymmetric pattern remains unknown. In this report, we describe realization deoxygenative unactivated (β-hydroxy ketone) bromide presence NHC activating agent. The approach can accommodate substituents various sizes functional groups, its synthetic potency demonstrated through gram scale reaction derivatizations into other compound families. Finally, apply our convergent synthesis four β-aryl ketones that are natural products or bioactive
Language: Английский
Citations
7
Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3097 - 3102
Published: April 4, 2024
This study introduces a novel approach involving XB-mediated cross-coupling of α-trifluoromethylated alkyl bromides with coumarins and quinolinones under visible light irradiation. Both density functional theory (DFT) calculations experimental studies converge to suggest that the noncovalent interaction between DMAP, intensified by α-trifluoromethyl group, plays pivotal role in facilitating this chemoselective reaction.
Language: Английский
Citations
4
Chemical Communications, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 1, 2025
We present a highly efficient and versatile nickel-catalyzed protocol for the reductive cross-coupling of unactivated CF2H-substituted electrophiles with wide variety aryl alkenyl halides. This novel approach offers high catalytic reactivity broad functional group compatibility, enabling late-stage fluoroalkylation drug molecules.
Language: Английский
Citations
0
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: April 1, 2025
Introducing fluorine atoms or fluorine-containing groups into drug molecules has become a common approach in design, with the incorporation of trifluoromethyl as focal point research field organic fluorochemistry. Here, we describe nickel-catalyzed hydrotrifluoromethylation internal alkynes alkyl bromides to synthesize series highly regioselective allyl trisubstituted alkenes. This reaction is characterized by mild conditions and broad functional-group tolerance, providing an efficient practical
Language: Английский
Citations
0
ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6555 - 6562
Published: April 7, 2025
Language: Английский
Citations
0