Nickel-Catalyzed Migratory Cross-Coupling Reactions: New Opportunities for Selective C–H Functionalization

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(23), P. 3475 - 3491

Published: Nov. 16, 2023

ConspectusMigratory cross-coupling via metal migration is a process of significant academic and industrial interest. It provides an attractive alternative for the selective installation functional group at remote C-H positions from simple precursors, thus enabling direct synthesis challenging structures not accessible with traditional cross-coupling. In particular, merger 1,n-Ni/H shift nickel, Ni-catalyzed migratory functionalization precursors has undergone particularly intense development emerged as valuable field research in past few years. This Account will outline recent progress made this arena terms migration-functionalization modes, diverse functionalizations, strategies regio- stereocontrol. Mechanistic studies synthetic applications are also discussed.In detail, we systematically categorize our work into two parts based on modes. first part, platform created sp3 alkenes or alkyl halides iterative 1,2-Ni/H shift-selective The key reactive Ni(II)H species chain-walking could be generated situ either polarity-reversed fashion relying stoichiometric reductants (X-Ni(II)-H) redox-neutral participation nucleophilic coupling partners (FG-Ni(II)-H). One advantage associated NiH system use relatively stable, abundant, safe olefin surrogates instead sensitive organometallics required reactions. Another that including carbonation more amination thiolation smoothly achieved suitable electrophiles their precursors. Finally, to address multifaceted selectivity reactivity issues asymmetric reactions, have developed feasible ligand relay catalytic strategy. dynamic exchange process, one promotes rapid while other highly stereoselective coupling. innovative strategy overcomes formidable challenge stemming difficulty designing single efficiently promote both steps second new sp2 1,4-Ni/H been reported. Starting readily available aryl vinyl partners, situ-generated aryl- vinylnickel(II) undergo reversible along backbone, subsequent various would allow access 1,4-migratory products. success was discovery appropriate A vinyl-to-aryl successfully enables modular ipso/ortho difunctionalization aryl-to-vinyl functionalized trisubstituted alkenes.We hope inspire broad interest future We strongly believe continued efforts fascinating overcome many remaining challenges, cutting-edge ligand/catalyst design enhance selectivity, conceptually modes additional transformations, in-depth mechanistic rational reaction design.

Language: Английский

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C(sp²)–H Hydroxylation via Catalytic 1,4-Ni Migration with N₂O

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(32), P. 17564 - 17569

Published: Aug. 2, 2023

Herein, we report a Ni-catalyzed C(sp2)-H hydroxylation of aryl bromides with N2O as an oxygen-atom donor. The reaction is enabled by 1,4-Ni translocation that results in ipso/ortho difunctionalized products. Regioselectivity and stereocontrol are dictated judicious choice the ligand backbone, thus giving access to either carbonyl or phenol derivatives offering opportunity repurpose hazardous substances en route valuable oxygen-containing building blocks.

Language: Английский

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Spatial Coupling of Photocatalytic CO₂ Reduction and Selective Oxidation on Covalent Triazine Framework/ZnIn₂S₄ Core–Shell Structures

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 25, 2024

Abstract Photocatalytic CO 2 reduction coupled with alcohol oxidation to aldehyde presents a promising strategy for the simultaneous production of fuels and valuable chemicals. The efficiency photocatalytic reactions remains low due poor charge separation, difficulty in activation, uncontrolled compatibility between reactions. This work S‐bridged covalent triazine framework (SCTF) core‐ZnIn S 4 shell photocatalysts selective furfural synthesis at distinct active sites. As evidenced by situ X‐ray photoelectron spectroscopy Kelvin probe force microscopy, photogenerated electrons composite transfer from ZnIn SCTF core, improving separation. Experimental theoretical results confirm that presence pyridine N atoms (Lewis basic sites) enhances adsorption, thereby reducing energy barrier *COOH generation promoting *CO production. Meanwhile, furfuryl deprotonation occur on consuming holes, which turn benefits conversion CO. result, optimized SCTF/ZnIn ‐0.2 core/shell photocatalyst exhibited superior yield 263.5 µmol g −1 95% under simulated sunlight irradiation.

Language: Английский

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Highly Stereoselective Synthesis of 1,3‐Enynes via Aryl to Vinyl 1,4‐Palladium Migration/Sonogashira Coupling Sequence

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(16)

Published: April 12, 2024

Abstract Alkynylation of alkenyl bromoarenes via aryl to vinyl 1,4‐palladium migration/copper‐free Sonogashira coupling sequence has been developed. This approach provides a facile methodology for the highly stereoselective synthesis multi‐substituted 1,3‐enynes in good excellent yields and regioselectivities.

Language: Английский

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Nickel‐Catalyzed Reductive Amidation of Aryl Sulfonium Salts with Isocyanates for Amide Synthesis via C−S Bond Activation

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: June 28, 2024

Abstract A nickel‐catalyzed reductive amidation of aryl sulfonium salts with isocyanates for amide synthesis via C−S bond cleavage was developed. The reactions proceeded smoothly at ambient temperature in the presence nickel catalyst and manganese metal DMF to give a variety amides moderate good yields wide functional group tolerance.

Language: Английский

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Copper-Catalyzed Regio- and Stereoselective Formal Hydro(borylmethylsilyl)ation of Internal Alkynes via Alkenyl-to-Alkyl 1,4-Copper Migration

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(43), P. 23470 - 23477

Published: Oct. 18, 2023

Catalytic reactions involving 1,n-metal migration from carbon to enable a nonclassical way of constructing organic molecular skeletons, rapidly providing complex molecules relatively simple precursors. By utilization this attractive feature, new and efficient synthesis alkenylsilylmethylboronates has been developed by formal hydro(borylmethylsilyl)ation unsymmetric internal alkynes with silylboronates under copper catalysis. The reaction proceeds regioselectively involves an unprecedented alkenyl-to-alkyl 1,4-copper migration. mechanism investigated series kinetic, NMR, deuterium-labeling experiments.

Language: Английский

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Stereoselective Synthesis of Conjugated Dienes via Aryl-to-Vinyl 1,4-Nickel Migration and Reductive Cross-Coupling

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

Published: Feb. 3, 2025

Selective functionalization of remote C-H bonds via metal/hydride shift and cross-coupling represents a powerful strategy in modern synthetic chemistry. Herein, we report highly efficient aryl-to-vinyl 1,4-nickel migration coupled with reductive for the stereoselective synthesis conjugated dienes. This tandem process proceeds under mild conditions, accommodates wide range substrates, achieves excellent regioselectivity Z/E stereoselectivity, offering valuable method constructing multisubstituted

Language: Английский

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Nickel-Catalyzed Hydrocarbamoylation of Alkenes with Isocyanates

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

Published: March 17, 2025

The hydrocarbamoylation of alkenes with isocyanates is a promising method for synthesizing amides. However, applying this strategy to more inert, simple alkenes, such as styrenes, α-olefins, and internal poses significant challenges. Here, we report the first nickel-catalyzed isocyanates, facilitated by triethoxysilane reduce nickelacycle intermediates. By switching ligands─including 6,6′-dimethyl-2,2′-bipyridine N-heterocyclic carbene─this efficiently produces amides from diverse array including gaseous olefins.

Language: Английский

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Visible Light Catalyzed Reductive Cross‐Coupling of α‐CF₃‐alkyl Bromide and Alkynyl Bromide^†

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(20), P. 2479 - 2484

Published: June 21, 2024

Comprehensive Summary Traditional reduction coupling reactions of two bromides typically rely on transition metal catalysis. Here, we introduce the development a visible‐light catalytic direct reaction between α ‐CF 3 ‐alkyl and alkynyl to access valuable organic frameworks. Our research confirms excellent compatibility this with various functional groups, which could be used modify substrate biologically active molecular fragments. Mechanistic investigations, including control experiments, fluorescence quenching studies, light‐switching have provided insights into mechanism. This study paves way for application catalysis in diverse synthetic transformations, offering sustainable efficient approach synthesis.

Language: Английский

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Nickel-Catalyzed Reductive Amidation of Aryl Fluorosulfates with Isocyanates: Synthesis of Amides via C–O Bond Cleavage

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 30, 2024

With the assistance of nickel as catalyst, 2,2'-bipyridine (bpy) ligand, and manganese reducing metal, reductive amidation isocyanates with readily accessible aryl fluorosulfates could be successfully accomplished. The reactions proceeded effectively via C-O bond activation in DMF at room temperature, enabling facile synthesis a range structurally diverse amides moderate to high yields broad functionality compatibility. In addition, synthetic usefulness method was further demonstrated by applying reaction scale-up late-stage functionalization complex molecules biological activities.

Language: Английский

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