Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp³)–H Bonds

Chemical Reviews, Год журнала: 2021, Номер 121(24), С. 14957 - 15074

Опубликована: Окт. 29, 2021

Transition-metal-catalyzed, coordination-assisted C(sp3)–H functionalization has revolutionized synthetic planning over the past few decades as use of these directing groups allowed for increased access to many strategic positions in organic molecules. Nonetheless, several challenges remain preeminent, such requirement high temperatures, difficulty removing or converting groups, and, although metals provide some reactivity, employing outside palladium. This review aims give a comprehensive overview coordination-assisted, transition-metal-catalyzed, direct nonactivated bonds by covering literature since 2004 order demonstrate current state-of-the-art methods well limitations. For clarity, this been divided into nine sections transition metal catalyst with subdivisions type bond formation. Synthetic applications and reaction mechanism are discussed where appropriate.

Язык: Английский

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Introduction: CH Activation

Chemical Reviews, Год журнала: 2017, Номер 117(13), С. 8481 - 8482

Опубликована: Июль 12, 2017

ADVERTISEMENT RETURN TO ISSUEEditorialNEXTIntroduction: CH ActivationRobert H. Crabtree and Aiwen LeiView Author Information Yale University Wuhan UniversityCite this: Chem. Rev. 2017, 117, 13, 8481–8482Publication Date (Web):July 12, 2017Publication History Published online12 July 2017Published inissue 12 2017https://pubs.acs.org/doi/10.1021/acs.chemrev.7b00307https://doi.org/10.1021/acs.chemrev.7b00307editorialACS PublicationsCopyright © 2017 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions free to access through this site. Learn MoreArticle Views39442Altmetric-Citations261LEARN 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 by 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 (2 MB) Get e-AlertscloseSUBJECTS:Alcohols,Functionalization,Hydrocarbons,Metals,Palladium e-Alerts

Язык: Английский

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Accessing Remote meta‐ and para‐C(sp²)−H Bonds with Covalently Attached Directing Groups

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(32), С. 10820 - 10843

Опубликована: Ноя. 29, 2018

Directing group assisted ortho-C-H activation has been known for the last few decades. In contrast, extending same approach to achieve of distal meta- and para-C-H bonds in aromatic molecules remained elusive a long time. The main challenge is conception macrocyclic transition state, which needed anchor metal catalyst close target bond. Judicious modification chain length, tether linkage, nature catalyst-coordinating donor atom led number successful studies years. This Review compiles significant achievements made this field both para-selectivity using covalently attached directing groups, are systematically classified on basis their mode covalent attachment substrate as well chemical nature. aims create more heuristic recognizing suitability groups use future organic transformations.

Язык: Английский

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Difunctionalization of Alkenes Involving Metal Migration

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(21), С. 7990 - 8003

Опубликована: Дек. 4, 2019

The direct difunctionalization of alkenes, a cheap and abundant feedstock, represents one the most attractive strategies for increasing molecular complexity in synthetic organic chemistry. In contrast with 1,2-difunctionalization recent advances showcase alkene 1,n-difunctionalizations (n≠2) involving metal migration is an emerging rapidly growing area research. This promising strategy not only opens novel avenue future development transformations, but also significantly expands upon bond disconnections available modern synthesis. Minireview summarizes progress migratory emphasis on driving force migration.

Язык: Английский

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Enantioselective C(sp³)–H Amidation of Thioamides Catalyzed by a Cobalt^III/Chiral Carboxylic Acid Hybrid System

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(4), С. 1153 - 1157

Опубликована: Ноя. 27, 2018

Abstract Recent advances in Cp x M III catalysis (M=Co, Rh, Ir) have enabled a variety of enantioselective C(sp 2 )−H functionalization reactions, but 3 is still largely unexplored. We describe an asymmetric amidation thioamides using achiral Co /chiral carboxylic acid hybrid catalytic system, which provides easy and straightforward access to chiral β‐amino thiocarbonyl carbonyl building blocks with quaternary carbon stereocenter.

Язык: Английский

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Catalytic alkylation of unactivated C(sp³)–H bonds for C(sp³)–C(sp³) bond formation

Chemical Society Reviews, Год журнала: 2019, Номер 48(18), С. 4921 - 4942

Опубликована: Янв. 1, 2019

This review summarizes recent advancements in catalytic direct transformation of unactivated C(sp³)–H bonds into C(sp³)–C(sp³) bonds.

Язык: Английский

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Electrochemical C−H/N−H Activation by Water‐Tolerant Cobalt Catalysis at Room Temperature

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(9), С. 2383 - 2387

Опубликована: Янв. 10, 2018

Electrochemistry enabled C-H/N-H functionalizations at room temperature by external oxidant-free cobalt catalysis. Thus, the sustainable electrocatalysis manifold proceeds with excellent levels of chemoselectivity and positional selectivity, ample scope, thus allowing electrochemical C-H activation under exceedingly mild reaction conditions in water.

Язык: Английский

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Exploiting hexafluoroisopropanol (HFIP) in Lewis and Brønsted acid-catalyzed reactions

Chemical Communications, Год журнала: 2020, Номер 56(78), С. 11548 - 11564

Опубликована: Янв. 1, 2020

Hexafluoroisopropanol (HFIP) is a solvent with unique properties that has recently gained attention for promoting wide range of challenging chemical reactions. It was initially believed HFIP almost exclusively involved in the stabilization cationic intermediates, owing to its high polarity and low nucleophilicity. However, many cases, mechanism action appears be more complex. Recent findings reveal Lewis Brønsted acid-catalyzed transformations conducted additionally involve cooperation between catalyst hydrogen-bond clusters, akin Lewis- or acid-assisted-Brønsted acid catalysis. This feature article showcases remarkable versatility reactions, an emphasis on examples yielding mechanistic insight.

Язык: Английский

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Asymmetric hydrofunctionalization of minimally functionalized alkenesviaearth abundant transition metal catalysis

Organic Chemistry Frontiers, Год журнала: 2017, Номер 5(2), С. 260 - 272

Опубликована: Сен. 27, 2017

The development of earth-abundant transition metal-catalysed highly enantioselective hydrofunctionalization minimally functionalized alkenes was summarized.

Язык: Английский

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A Perspective on Late-Stage Aromatic C–H Bond Functionalization

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(6), С. 2399 - 2414

Опубликована: Янв. 27, 2022

Late-stage functionalization of C-H bonds (C-H LSF) can provide a straightforward approach to the efficient synthesis functionalized complex molecules. However, LSF is challenging because bond must be in presence various other functional groups. In this Perspective, we evaluate aromatic on basis four criteria─reactivity, chemoselectivity, site-selectivity, and substrate scope─and our own views current challenges as well promising strategies areas growth going forward.

Язык: Английский

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