Asymmetric multi-component trifunctionalization reactions with α-Halo Rh-carbenes DOI Creative Commons

Xiaoyan Yang,

Xiaoyu Zhou, Wenhao Hu

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 7, 2025

Multi-component multi-functionalization reactions involving active intermediates are powerful tools for rapidly generating a wide array of compounds. Metal carbynoids, with their distinct reactivity, hold great promise developing synthetic methodologies. However, application in catalytic transfer has been hindered by the limited availability suitable precursors. In this study, we investigate potential α-halo Rh-carbenes, leveraging concept metal carbynoids reactions. Through chiral phosphoric acid-catalyzed asymmetric trifunctionalization, have developed method synthesizing variety α-cyclic ketal β-amino esters high yields and excellent enantioselectivity. Our extensive experimental computational studies reveal that Rh-carbenes exhibit carbynoid properties, which facilitate transformation into functionalized Fischer-type through decomposition C-halo bond.

Language: Английский

Catalytic three-component dicarbofunctionalization reactions involving radical capture by nickel DOI
Shengqing Zhu, Xian Zhao, Huan Li

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(19), P. 10836 - 10856

Published: Jan. 1, 2021

The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction complex motifs. Despite remarkable progress, novel and efficient methods achieving such transformations under milder conditions with chemo-, regio-, stereoselectivity still remain significant challenge; thus, their development is highly desirable. Recently, merging nickel catalysis radical chemistry offers new benign unprecedented reactivity selectivity. In this review, we summarize recent advances in area by underpinning domino involving capture to provide clear overview reaction designs mechanistic scenarios.

Language: Английский

Citations

248
Electrochemically driven cross-electrophile coupling of alkyl halides DOI
Wen Zhang, Lingxiang Lu,

Wendy Zhang

et al.

Nature, Journal Year: 2022, Volume and Issue: 604(7905), P. 292 - 297

Published: Feb. 21, 2022

Language: Английский

Citations

237
Nickel and Palladium Catalysis: Stronger Demand than Ever DOI
Victor M. Chernyshev, Valentine P. Ananikov

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

Citations

157
Controlling Ni redox states by dynamic ligand exchange for electroreductive Csp3–Csp2 coupling DOI
Taylor B. Hamby, Matthew J. LaLama, Christo S. Sevov

et al.

Science, Journal Year: 2022, Volume and Issue: 376(6591), P. 410 - 416

Published: April 21, 2022

Cross-electrophile coupling (XEC) reactions of aryl and alkyl electrophiles are appealing but limited to specific substrate classes. Here, we report electroreductive XEC previously incompatible including tertiary bromides, chlorides, aryl/vinyl triflates. Reactions rely on the merger an electrochemically active complex that selectively reacts with bromides through 1e

Language: Английский

Citations

139
Streamlined Alkylation via Nickel-Hydride-Catalyzed Hydrocarbonation of Alkenes DOI
Zhikun Zhang, Srikrishna Bera, Chao Fan

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(16), P. 7015 - 7029

Published: April 12, 2022

Compounds rich in sp3-hybridized carbons are desirable drug discovery. Nickel-catalyzed hydrocarbonation of alkenes is a potentially efficient method to synthesize these compounds. By using abundant, readily available, and stable as pro-nucleophiles, reactions can have broad scope high functional group tolerance. However, this methodology still an early stage development, the first examples were reported only 2016. Herein, we summarize progress emerging field, with emphasis on enantioselective reactions. We highlight major developments, critically discuss wide range possible mechanisms, offer our perspective state challenges field. hope Perspective will stimulate future works area, making widely applicable organic synthesis.

Language: Английский

Citations

131
Carbene and photocatalyst-catalyzed decarboxylative radical coupling of carboxylic acids and acyl imidazoles to form ketones DOI Creative Commons
Shi‐Chao Ren, Xing Yang, Bivas Mondal

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 23, 2022

The carbene and photocatalyst co-catalyzed radical coupling of acyl electrophile a precursor is emerging as attractive method for ketone synthesis. However, previous reports mainly limited to prefunctionalized precursors two-component coupling. Herein, an N-heterocyclic catalyzed decarboxylative carboxylic acids imidazoles disclosed, in which the are directly used precursors. could also be generated situ by reaction acid with CDI thus furnishing formally two acids. In addition, successfully extended three-component using alkene third partner via relay process. mild conditions, operational simplicity, use reacting partners make our powerful strategy construction complex ketones from readily available starting materials, late-stage modification natural products medicines.

Language: Английский

Citations

86
Nickel Catalysis via SH2 Homolytic Substitution: The Double Decarboxylative Cross-Coupling of Aliphatic Acids DOI
Artem V. Tsymbal, Lorenzo Delarue Bizzini, David W. C. MacMillan

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(46), P. 21278 - 21286

Published: Nov. 14, 2022

Cross-coupling platforms are traditionally built around a sequence of closed-shell steps, such as oxidative addition, transmetalation, and reductive elimination. Herein, we describe dual photo/nickel catalytic manifold that performs cross-coupling via complementary involving free radical generation, sorting selective binding to Ni(II) center, bimolecular homolytic substitution (SH2) at high-valent nickel-alkyl complex. This enables the hitherto elusive diverse aliphatic carboxylic acids generate valuable C(sp3)-C(sp3)-products. Notably, powerful SH2 mechanism provides general access sterically encumbered quaternary carbon centers, addressing long-standing challenge in fragment coupling chemistry.

Language: Английский

Citations

79
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

73
Engaging Alkenes in Metallaphotoredox: A Triple Catalytic, Radical Sorting Approach to Olefin-Alcohol Cross-Coupling DOI
Qinyan Cai, Iona M. McWhinnie, Nathan W. Dow

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(18), P. 12300 - 12309

Published: April 24, 2024

Metallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via single-electron reactivity. Correspondingly, expanding metallaphotoredox to encompass new C(

Language: Английский

Citations

21
Facile Access to Quaternary Carbon Centers via Ni-Catalyzed Arylation of Alkenes with Organoborons DOI
Zi-Chao Wang, Lei Gao, Songyang Liu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

Quaternary carbon centers are widespread structural motifs, thus representing extensive interest in organic synthesis. We describe here an efficient nickel-catalyzed intermolecular, Markovnikov-selective arylation of minimally functionalized alkenes with stable organoborons, affording a broad range cyclic or acyclic quaternary under mild conditions. The utilization the diimine ligand is critical for high reactivity and chemoselectivity. Furthermore, using bulky chiral as Ni catalyst, stereocenters can be readily prepared levels enantiocontrol. Mechanism studies suggest that, before protonation, rare nickel shift from alkyl to aryl might occur.

Language: Английский

Citations

3