Photoactive electron donor–acceptor complex platform for Ni-mediated C(sp³)–C(sp²) bond formation

Chemical Science, Год журнала: 2021, Номер 12(15), С. 5450 - 5457

Опубликована: Янв. 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.

Язык: Английский

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Multimetallic-Catalyzed C–C Bond-Forming Reactions: From Serendipity to Strategy

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(12), С. 6596 - 6614

Опубликована: Март 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.

Язык: Английский

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Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 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

Язык: Английский

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Computational Methods Enable the Prediction of Improved Catalysts for Nickel-Catalyzed Cross-Electrophile Coupling

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3043 - 3051

Опубликована: Янв. 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.

Язык: Английский

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In-Situ Bromination Enables Formal Cross-Electrophile Coupling of Alcohols with Aryl and Alkenyl Halides

ACS Catalysis, Год журнала: 2021, Номер 12(1), С. 580 - 586

Опубликована: Дек. 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

Язык: Английский

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The application of modern reactions in large-scale synthesis

Nature Reviews Chemistry, Год журнала: 2021, Номер 5(8), С. 546 - 563

Опубликована: Июнь 22, 2021

Язык: Английский

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Unlocking the Friedel-Crafts arylation of primary aliphatic alcohols and epoxides driven by hexafluoroisopropanol

Chem, Год журнала: 2021, Номер 7(12), С. 3425 - 3441

Опубликована: Ноя. 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.

Язык: Английский

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Zinc-free, Scalable Reductive Cross-Electrophile Coupling Driven by Electrochemistry in an Undivided Cell

ACS Catalysis, Год журнала: 2022, Номер 12(20), С. 12617 - 12626

Опубликована: Окт. 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-

Язык: Английский

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Homogeneous Organic Electron Donors in Nickel-Catalyzed Reductive Transformations

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(12), С. 7589 - 7609

Опубликована: Июнь 7, 2022

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

Язык: Английский

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Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(20), С. 10930 - 10937

Опубликована: Май 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

Язык: Английский

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