Tri-Molecular Homolytic Combination Mechanism for Carbon–Halogen Bond Activation in Ni/Co Synergistic Catalysis DOI
Rong-Wan Gao, Lin-Yan Bao, Shuang Wang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4307 - 4316

Published: Feb. 25, 2025

Language: Английский

Photoactive electron donor–acceptor complex platform for Ni-mediated C(sp3)–C(sp2) bond formation DOI Creative Commons
Lisa Marie Kammer, Shorouk O. Badir,

Ren‐Ming Hu

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(15), P. 5450 - 5457

Published: Jan. 1, 2021

This works demonstrates the implementation of an electron donor–acceptor (EDA) complex platform toward Ni-catalyzed C(sp3)–C(sp2) bond formation, circumventing need for exogenous photocatalysts, additives, and stoichiometric metal reductants.

Language: Английский

Citations

124
Multimetallic-Catalyzed C–C Bond-Forming Reactions: From Serendipity to Strategy DOI
Laura K. G. Ackerman, Stavros K. Kariofillis, Daniel J. Weix

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6596 - 6614

Published: March 13, 2023

The use of two or more metal catalysts in a reaction is powerful synthetic strategy to access complex targets efficiently and selectively from simple starting materials. While capable uniting distinct reactivities, the principles governing multimetallic catalysis are not always intuitive, making discovery optimization new reactions challenging. Here, we outline our perspective on design elements using precedent well-documented C–C bond-forming reactions. These strategies provide insight into synergy compatibility individual components reaction. Advantages limitations discussed promote further development field.

Language: Английский

Citations

54
Computational Methods Enable the Prediction of Improved Catalysts for Nickel-Catalyzed Cross-Electrophile Coupling DOI
Michelle E. Akana,

Sergei Tcyrulnikov,

Brett D. Akana-Schneider

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3043 - 3051

Published: Jan. 26, 2024

Cross-electrophile coupling has emerged as an attractive and efficient method for the synthesis of C(sp2)–C(sp3) bonds. These reactions are most often catalyzed by nickel complexes nitrogenous ligands, especially 2,2′-bipyridines. Precise prediction, selection, design optimal ligands remains challenging, despite significant increases in reaction scope mechanistic understanding. Molecular parameterization statistical modeling provide a path to development improved bipyridine that will enhance selectivity existing broaden electrophiles can be coupled. Herein, we describe generation computational ligand library, correlation observed outcomes with features silico Ni-catalyzed cross-electrophile coupling. The new nitrogen-substituted display 5-fold increase product formation versus homodimerization when compared current state art. This yield was general several couplings, including challenging aryl chloride N-alkylpyridinium salt.

Language: Английский

Citations

20
Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis DOI Creative Commons
Lauren E. Ehehalt, Omar M. Beleh, Isabella C. Priest

et al.

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
In-Situ Bromination Enables Formal Cross-Electrophile Coupling of Alcohols with Aryl and Alkenyl Halides DOI
K. Benjamin, Jonas K. Widness, Michael M. Gilbert

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 12(1), P. 580 - 586

Published: Dec. 21, 2021

Although alcohols are one of the largest pools alkyl substrates, approaches to utilize them in cross-coupling and cross-electrophile coupling limited. We report use 1° 2° with aryl vinyl halides form C(sp

Language: Английский

Citations

79
The application of modern reactions in large-scale synthesis DOI
Kaitlyn Lovato, Patrick S. Fier, Kevin M. Maloney

et al.

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(8), P. 546 - 563

Published: June 22, 2021

Language: Английский

Citations

73
Unlocking the Friedel-Crafts arylation of primary aliphatic alcohols and epoxides driven by hexafluoroisopropanol DOI Creative Commons
Shaofei Zhang, Marie Vayer,

Florent Noël

et al.

Chem, Journal Year: 2021, Volume and Issue: 7(12), P. 3425 - 3441

Published: Nov. 17, 2021

Alcohols and epoxides are arguably ideal electrophiles for the Friedel-Crafts alkylation, since they widely available, require no pre-activation, produce stoichiometric waste beyond water. However, neither primary aliphatic alcohols nor most classes of terminal compatible with existing intermolecular methodologies, sequential reactions starting from consequently remain underexplored. Here, we report that these limitations easily overcome using Brønsted acid catalysis in hexafluoroisopropanol (HFIP) as a solvent. Electron-poor aromatic undergo stereospecific arylation to give an alcohol which, depending on reaction conditions, can partake second nucleophilic substitution different arene one pot. Phenyl ethanols react through phenonium intermediate, whereas simple participate rare SN2 process, delivering linear products exclusively. This work provides alternative metal-catalyzed cross-couplings accessing important scaffolds, widening range applications reaction.

Language: Английский

Citations

68
Zinc-free, Scalable Reductive Cross-Electrophile Coupling Driven by Electrochemistry in an Undivided Cell DOI
Mareena C. Franke,

Victoria Longley,

Mohammad Rafiee

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(20), P. 12617 - 12626

Published: Oct. 3, 2022

Nickel-catalyzed reductive cross-electrophile coupling reactions are becoming increasingly important in organic synthesis, but application at scale is limited by three interconnected challenges: a reliance on amide solvents (complicated workup, regulated), the generation of stoichiometric Zn salts isolation, waste disposal issue), and mixing/activation challenges zinc powder. We show here an electrochemical approach that addresses these issues: reaction works acetonitrile with diisopropylethylamine as terminal reductant simple undivided cell (graphite(+)/nickel foam(-)). The utilizes combination two ligands, 4,4'-di-

Language: Английский

Citations

66
Homogeneous Organic Electron Donors in Nickel-Catalyzed Reductive Transformations DOI
David J. Charboneau, Nilay Hazari,

Haotian Huang

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(12), P. 7589 - 7609

Published: June 7, 2022

Many contemporary organic transformations, such as Ni-catalyzed cross-electrophile coupling (XEC), require a reductant. Typically, heterogeneous reductants, Zn

Language: Английский

Citations

40
Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp3–sp2 Carbon–Carbon Bonds DOI Creative Commons
James L. Douthwaite, Ruheng Zhao, Eunjae Shim

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 10930 - 10937

Published: May 15, 2023

Amines and carboxylic acids are abundant synthetic building blocks that classically united to form an amide bond. To access new pockets of chemical space, we interested in the development amine-acid coupling reactions complement coupling. In particular, formation carbon-carbon bonds by formal deamination decarboxylation would be impactful addition synthesis toolbox. Here, report a cross-coupling alkyl amines aryl C(sp

Language: Английский

Citations

29