Organic Letters, Journal Year: 2023, Volume and Issue: 25(46), P. 8344 - 8349
Published: Nov. 14, 2023
A nickel-catalyzed three-component alkylarylation of alkenyl N-heteroarenes with α-bromocarboxylates and aryl boronic acids is reported. The protocol provides a new method to access variety N-heteroarene substituted diarylalkanes in moderate good yields. It features mild reaction conditions, cheap nickel catalyst, readily available substrates, broad substrate scope.
Language: Английский
Nature, Journal Year: 2024, Volume and Issue: 628(8006), P. 104 - 109
Published: Feb. 13, 2024
Language: Английский
Citations
40
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Feb. 17, 2024
Abstract Transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts metal reductant and the requirement installing directing group to suppress inherent β-H elimination bring great limitations this type reaction. We demonstrate herein that two different accessible via radical-anion relay Na 2 S O 4 as both sulfone-source. The together electron-shuttle catalyst crucial divert mechanistic pathway toward formation sulfone anion instead previously reported alkylmetal intermediates. Mechanistic studies allow identification carbon-centered radical sulfur-centered radical, which are in equilibrium capture or extrusion SO could be converted accelerated by iron catalysis, leading observed high chemoselectivity.
Language: Английский
Citations
25
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
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(2), P. 1667 - 1676
Published: Jan. 7, 2025
We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides alkylzinc reagents. The reaction is enabled by amine coordination can use all primary, secondary, tertiary amines. constructs two new C(sp3)-C(sp3) C(sp3)-C(sp2) bonds produces δ- ε-arylamines C(sp3)-branching at the γ- δ-positions. A variety heteroaryl iodides both primary secondary reagents be used as coupling carbon sources. Mechanistic studies suggest that cooperative effect organic nitriles electron-deficient (EDAs) ligands.
Language: Английский
Citations
1
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)
Published: April 8, 2024
We here reported a highly stereoselective method for the synthesis of polysubstituted conjugated dienes from α-aryl α-diazo alkynyl ketones and pyrazole-substituted unsymmetric aminals under mild conditions, which was promoted by photo-irridation involved with 1,6-dipolar intermediate quadruple sigmatropic rearrangements, successfully developed. In this transformation, cleavage four bonds recombination five were implemented in one operational step. This protocol provided modular tool constructing amines, pyrazoles α-alkynyl-α-diazoketones one-pot manner. The results mechanistic investigation indicated that plausible reaction path underwent 1,6-sigmatropic rearrangement instead 1,5-sigmatropic rearrangement.
Language: Английский
Citations
6
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Sept. 10, 2024
Language: Английский
Citations
5
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7210 - 7215
Published: March 4, 2024
Transition metal-catalyzed reductive cross-couplings to build C–C/Si bonds have been developed, but the cross-coupling create C(sp2)–B bond has not explored. Herein, we describe a nickel-catalyzed between aryl halides and bromoboranes construct bond. This protocol offers convenient approach for synthesis of wide range boronate esters, using readily available starting materials. Mechanistic studies indicate that key success reaction is activation B–Br with Lewis base such as 2-MeO-py. The ensures will react active nickel(I) catalyst prior halides, which different from sequence general C(sp2)–C/Si cross-coupling, where oxidative addition an halide proceeds first. Notably, this minimizes production undesired homocoupling byproduct without requirement excessive quantities either substrate.
Language: Английский
Citations
5
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Nov. 28, 2024
The transition metal-catalysed dicarbofunctionalisation of unactivated alkenes normally requires exogenous strong coordinated directing groups, thus reducing the overall reaction efficiency. Here, we report a ligand-enabled Ni(II)-catalysed with aryl/alkenyl boronic acids and alkyl halides as coupling partners diverse range native functional groups group. This protocol provides an efficient direct route towards vicinal 1,2-disubstituted alkanes using primary, secondary, tertiary amides, sulfonamides, well secondary amines under redox-neutral conditions that are challenging to access through conventional methods. key success this is use bulky β-diketone ligand, which could enable insertion alkene aryl-Ni(II) species, stabilize alkyl-Ni(II) species inhibit homolytic cleavage, supporting by both experimental computational studies. features group, broad substrate scope, excellent scalability. groups. authors
Language: Английский
Citations
5
Organic Letters, Journal Year: 2024, Volume and Issue: 26(21), P. 4532 - 4536
Published: May 21, 2024
A binary Ni/Eu catalytic system has been developed, which enables an efficient reductive dicarbofunctionalization of unactivated alkenes with alkyl halides and malononitriles. The combination Ni electron-shuttle catalysis Eu(OTf)
Language: Английский
Citations
4
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)
Published: Sept. 18, 2023
The catalytic C(sp3 )-C(sp3 ) coupling of alkyl halides and tertiary amines offers a promising tool for the rapid decoration amine skeletons. However, this approach has not been well established, partially due to challenges in precisely distinguishing controlling reactivity amine-coupling partners their product homologues. Herein, we developed metal-free photocatalytic system aminomethylation through radical-involved bond formation, allowing synthesis sterically congested that are interest organic but easily prepared by other methods. Mechanistic studies disclosed hindered N-substituents key activate tuning redox potentials drive reaction forward.
Language: Английский
Citations
11