Nickel and Palladium Catalysis: Stronger Demand than Ever

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(2), P. 1180 - 1200

Published: Jan. 5, 2022

Key similarities and differences of Pd Ni in catalytic systems are discussed. Overall, catalyze a vast number similar C–C C–heteroatom bond-forming reactions. However, the smaller atomic radius lower electronegativity Ni, as well more negative redox potentials low-valent species, often provide higher reactivity oxidative addition or insertion reactions persistence alkyl-Ni intermediates against β-hydrogen elimination, thus enabling activation reluctant electrophiles, including alkyl electrophiles. Another key point relates to stability open-shell electronic configurations Ni(I) Ni(III) compared with Pd(I) Pd(III). Nickel very involve interconvertible Ni(n+) active species variable oxidation states (Ni(0), Ni(I), Ni(II), Ni(III)). In contrast, involving Pd(III) still relatively less developed may require facilitation by special ligands merging photo- electrocatalysis. high Pd(n+) ensure their facile reduction Pd(0) under assistance numerous reagents solvents, providing concentrations molecular Pd1(0) complexes that can reversibly aggregate into Pdn clusters nanoparticles form cocktail Pdn(0) various nuclearities (i.e., values "n"). Ni(0) strong reductants; they sensitive deactivation air other oxidizers and, consequence, operate at catalyst loadings than palladium same The ease robustness versatility for catalysis, whereas variety enables diverse uncommon reactivity, albeit requiring efforts stabilization nickel systems. As discussion, we note easily "cocktail particles" different but (Pd1, Pdn, NPs), behave species" is stable nuclearities. Undoubtedly, there stronger demand ever not only develop improved efficient catalysts also understand mechanisms

Language: Английский

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Recent Advances in Nickel-Catalyzed Three-Component Difunctionalization of Unactivated Alkenes

Synthesis, Journal Year: 2020, Volume and Issue: 52(09), P. 1346 - 1356

Published: March 2, 2020

Catalytic, intermolecular difunctionalization of alkenes represents an efficient and diverse protocol for the buildup molecular complexity from abundant materials by forging two chemical bonds in a single operation. Despite important progress this area, transition-metal-catalyzed three-component unactivated remains underdeveloped, mainly because low reactivity, reduced polarization, high tendency toward β-hydride elimination these compounds. In context, nickel-catalyzed, selective, methods that generally proceed via distinct reaction pathways, migratory insertion nickel species into radical addition to alkenes, have been developed. This short review highlights recent advances area. 1 Introduction 2 Nickel-Catalyzed Three-Component Difunctionalization Unactivated­ Alkenes Migratory Insertion Processes 3 Radical 4 Conclusions Perspectives

Language: Английский

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Site‐Selective 1,2‐Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(11), P. 4370 - 4374

Published: Jan. 7, 2020

A modular, site-selective 1,2-dicarbofunctionalization of vinyl boronates with organic halides through dual catalysis is described. This reaction proceeds under mild conditions and characterized by excellent chemo- regioselectivity. It thus represents a complementary new technique for preparing densely functionalized alkyl boron architectures from simple accessible precursors.

Language: Английский

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Carbon-centered radical capture at nickel(II) complexes: Spectroscopic evidence, rates, and selectivity

Chem, Journal Year: 2023, Volume and Issue: 9(5), P. 1295 - 1308

Published: March 13, 2023

Language: Английский

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Dual Nickel/Photoredox-Catalyzed Asymmetric Carbosulfonylation of Alkenes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(23), P. 12532 - 12540

Published: May 30, 2023

An asymmetric three-component carbosulfonylation of alkenes is presented here. The reaction, involving the simultaneous formation a C-C and C-S bond across π-system, uses dual nickel/photoredox catalytic system to produce both β-aryl β-alkenyl sulfones in high yields with excellent levels stereocontrol (up 99:1 er). This protocol exhibits broad substrate scope functional group tolerance its synthetic potential has been demonstrated by successful applications toward pharmacologically relevant molecules. A array control experiments supports involvement secondary alkyl radical intermediate generated through addition sulfonyl double bond. Moreover, stoichiometric cross-over further suggest an underlying Ni(0)/Ni(I)/Ni(III) pathway operative these transformations.

Language: Английский

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