Mechanisms of Nickel-Catalyzed Cross-Coupling Reactions

Trends in Chemistry, Год журнала: 2019, Номер 1(9), С. 830 - 844

Опубликована: Сен. 13, 2019

Язык: Английский

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Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

Chemical Reviews, Год журнала: 2018, Номер 119(4), С. 2453 - 2523

Опубликована: Окт. 30, 2018

Computational chemistry provides a versatile toolbox for studying mechanistic details of catalytic reactions and holds promise to deliver practical strategies enable the rational in silico catalyst design. The reactivity nontrivial electronic structure effects, common systems based on 3d transition metals, introduce additional complexity that may represent particular challenge standard computational strategies. In this review, we discuss challenges capabilities modern methods reaction mechanisms promoted by metal molecular catalysts. Particular focus will be placed ways addressing multiconfigurational problem calculations role expert bias utilization available methods. development density functionals designed address metals is also discussed. Special emphasis account solvation effects multicomponent nature systems. This followed an overview recent studies processes catalysts metals. Cases involve noninnocent ligands, systems, metal-ligand metal-metal cooperativity, as well modeling complex such metal-organic frameworks are presented. Conventionally, heavily dependent chemical intuition input researcher. Recent developments advanced automated path analysis hold eliminating human-bias from catalysis studies. A brief these approaches presented final section review. paper closed with general concluding remarks.

Язык: Английский

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Activation of C–O and C–N Bonds Using Non-Precious-Metal Catalysis

ACS Catalysis, Год журнала: 2020, Номер 10(20), С. 12109 - 12126

Опубликована: Сен. 10, 2020

ADVERTISEMENT RETURN TO ISSUEPREVViewpointNEXTActivation of C–O and C–N Bonds Using Non-Precious-Metal CatalysisTimothy B. BoitTimothy BoitDepartment Chemistry Biochemistry, University California, Los Angeles, California 90095, United StatesMore by Timothy Boit, Ana S. BulgerAna BulgerDepartment Bulger, Jacob E. DanderJacob DanderDepartment Dander, Neil K. Garg*Neil GargDepartment States*E-mail: [email protected]More Garghttp://orcid.org/0000-0002-7793-2629Cite this: ACS Catal. 2020, 10, 20, 12109–12126Publication Date (Web):September 2020Publication History Received30 July 2020Published online10 September inissue 16 October 2020https://pubs.acs.org/doi/10.1021/acscatal.0c03334https://doi.org/10.1021/acscatal.0c03334article-commentaryACS PublicationsCopyright © 2020 American Chemical Society. This publication is available under these Terms Use. Request reuse permissions free to access through this site. Learn MoreArticle Views15643Altmetric-Citations116LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated reflect usage leading up last few days.Citations number other articles citing article, calculated Crossref daily. Find more information about citation counts.The Altmetric Attention Score a quantitative measure attention that research has received online. Clicking on donut icon will load page at altmetric.com with additional details score social media presence for given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail (3 MB) Get e-AlertscloseSUBJECTS:Alkyls,Amides,Coupling reactions,Cross coupling reaction,Organic compounds e-Alerts

Язык: Английский

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Nickel(0)‐Catalyzed Hydroarylation of Styrenes and 1,3‐Dienes with Organoboron Compounds

Angewandte Chemie International Edition, Год журнала: 2017, Номер 57(2), С. 461 - 464

Опубликована: Ноя. 21, 2017

Abstract A Ni‐catalyzed hydroarylation of styrenes and 1,3‐dienes with organoboron compounds has been developed. The reaction offers a highly selective approach to diarylalkanes allylarenes under redox‐neutral conditions. In this reaction, new strategy that uses the proton methanol generate active catalyst species Ni−H was hydroarylation, combined Ir‐catalyzed C−H borylation, affords very efficient straightforward access retinoic acid receptor agonist.

Язык: Английский

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Preparation of Quaternary Centers via Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling of Tertiary Sulfones

Journal of the American Chemical Society, Год журнала: 2017, Номер 140(1), С. 78 - 81

Опубликована: Дек. 7, 2017

We describe the development of a nickel-catalyzed Suzuki–Miyaura cross-coupling tertiary benzylic and allylic sulfones with arylboroxines. A variety sulfones, which can easily be prepared via deprotonation–alkylation route, were reacted to afford symmetric unsymmetric quaternary products in good yields. highlight use either BrettPhos or Doyle's phosphines as effective ligands for these challenging desulfonative coupling reactions. The utility this methodology was demonstrated concise synthesis vitamin D receptor modulator analogue.

Язык: Английский

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Hydrogen Bonding Phase-Transfer Catalysis with Potassium Fluoride: Enantioselective Synthesis of β-Fluoroamines

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(7), С. 2878 - 2883

Опубликована: Янв. 28, 2019

Potassium fluoride (KF) is an ideal reagent for fluorination because it safe, easy to handle and low-cost. However, poor solubility in organic solvents coupled with limited strategies control its reactivity has discouraged use asymmetric C–F bond formation. Here, we demonstrate that hydrogen bonding phase-transfer catalysis KF provides access valuable β-fluoroamines high yields enantioselectivities. This methodology employs a chiral N-ethyl bis-urea catalyst brings solid into solution as tricoordinated urea-fluoride complex. operationally simple reaction affords enantioenriched fluoro-diphenidine (up 50 g scale) using 0.5 mol % of recoverable catalyst.

Язык: Английский

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Taming Nickel-Catalyzed Suzuki-Miyaura Coupling: A Mechanistic Focus on Boron-to-Nickel Transmetalation

ACS Catalysis, Год журнала: 2018, Номер 8(6), С. 4812 - 4823

Опубликована: Апрель 13, 2018

The mechanism of boron-to-nickel transmetalation, the key step nickel-catalyzed Suzuki-Miyaura (S-M) coupling, was examined both experimentally and theoretically. Dinuclear μ-hydroxo-bridged complexes formed by reaction trans-[ArNi(PR3)2X] with hydroxide are not directly involved in but they rather act as a resting state for catalyst. base/boronic acid ratio is crucial parameter, it modulates extent formation these dinuclear species thus tunes catalytic activity. These findings explain some limitations encountered practical applications S-M couplings suggest how to tailor experimental conditions order overcome difficulties.

Язык: Английский

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Multicatalytic Stereoselective Synthesis of Highly Substituted Alkenes by Sequential Isomerization/Cross-Coupling Reactions

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(13), С. 4743 - 4750

Опубликована: Март 21, 2018

Starting from readily available alkenyl methyl ethers, the stereoselective preparation of highly substituted alkenes by two complementary multicatalytic sequential isomerization/cross-coupling sequences is described. Both elementary steps these are challenging processes when considered independently. A cationic iridium catalyst was identified for isomerization allyl ethers and found to be compatible with a nickel subsequent cross-coupling in situ generated vinyl various Grignard reagents. The method sensitive functional groups multitude olefinic substitution patterns deliver products high control newly C═C bond. enantioselective variant this [Ir/Ni] sequence has been established using chiral precatalyst. [Pd/Ni] catalytic optimized remote final were isolated lower level stereocontrol. Upon proper choice reagent, we demonstrated that C(sp2)—C(sp2) C(sp2)—C(sp3) bonds can constructed both systems delivering would difficult access conventional methods.

Язык: Английский

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Forming Benzylic Iodides via a Nickel Catalyzed Diastereoselective Dearomative Carboiodination Reaction of Indoles

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(15), С. 5095 - 5099

Опубликована: Фев. 20, 2019

A diastereoselective dearomative carboiodination reaction is reported. We report a novel metal-catalyzed approach to install reactive secondary benzylic iodides. Utilizing the unique reactivity of nickel, we have expanded non-activated aromatic double bonds forming previously unattainable class also broadly applicable method avoid use metallic reducing agent by utilizing an alkyl phosphite as ligand. The thought proceed through syn intramolecular carbonickelation across 2-substituted indole followed diastereoretentive reductive elimination carbon-iodine bond. complex iodinated indolines generated in were obtained moderate good yields and excellent diastereoselectivity. products easily functionalized variety synthetic methods.

Язык: Английский

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Recent Advances in Theoretical Studies on Transition-Metal-Catalyzed Carbene Transformations

Accounts of Chemical Research, Год журнала: 2021, Номер 54(14), С. 2905 - 2915

Опубликована: Июль 7, 2021

ConspectusMetal carbene plays a vital role in modern organic synthesis. The neutral divalent carbon of metal renders it an active intermediate throughout range reactions. In experiments, diverse carbene-related transformation reactions have been established, including transition-metal-catalyzed cross-coupling using N-heterocyclic carbenes as ligands, insertion into σ bonds, cyclopropanations, ylide formation, and so forth. remarkable progress achieved synthetic chemistry, turn, has increased the demand for mechanistic studies chemistry. A thorough understanding reaction mechanisms can extend application scope compounds inspire rational design new reactions.Density functional theory (DFT) calculations performed our group to gain more insights This account focuses on computational with nucleophiles. generation or metal-ligated free subsequent pathways is discussed. According nucleophiles, three generalized models are summarized, intramolecular migratory carbene, intermolecular nucleophilic addition toward outer-sphere carbene.In general, mechanism commonly proposed since electrophilic carbon. From point view, also widely used because bonds formally occurs through this mechanism. An that form complex instead carbene. contains naked not coordinated center. case, transition-metal catalyst only Lewis acid, directly at Our results suggested facile step ligation could stabilize transition state well generated intermediate. low energy barrier due lack entropy penalty. Carbene formation from precursors usually rate-determining step, except addition, reactivity nucleophiles significant influence overall rate. We envision weak nucleophilicity would suppress addition. These showcase characteristics models, we hope will spur development

Язык: Английский

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