Mild metal-catalyzed C–H activation: examples and concepts

Chemical Society Reviews, Journal Year: 2016, Volume and Issue: 45(10), P. 2900 - 2936

Published: Jan. 1, 2016

C–H Activation reactions that proceed under mild conditions are more attractive for applications in complex molecule synthesis. Mild transformations reported since 2011 reviewed and the different concepts strategies have enabled their mildness discussed.

Language: Английский

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Transition metal-catalyzed C–H bond functionalizations by the use of diverse directing groups

Organic Chemistry Frontiers, Journal Year: 2015, Volume and Issue: 2(9), P. 1107 - 1295

Published: Jan. 1, 2015

In this review, a summary of transition metal-catalyzed C–H activation by utilizing the functionalities as directing groups is presented.

Language: Английский

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Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(3), P. 1788 - 1887

Published: Jan. 6, 2020

During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for expedient and siteselective construction of C–C bonds. Among various strategies, bidentate groups are now recognized as one most efficient devices selective functionalization certain positions due to fact its metal center permits fine, tunable, reversible coordination. The family permit types assistance be achieved, such N,N-dentate, N,O-dentate, N,S-dentate auxiliaries, which categorized based on coordination site. In this review, we broadly discuss bond reactions formation bonds with aid groups.

Language: Английский

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Undirected, Homogeneous C–H Bond Functionalization: Challenges and Opportunities

ACS Central Science, Journal Year: 2016, Volume and Issue: 2(5), P. 281 - 292

Published: May 2, 2016

The functionalization of C–H bonds has created new approaches to preparing organic molecules by enabling strategic "disconnections" during the planning a synthetic route. Such functionalizations also have ability derivatize complex modifying one or more many bonds. For these reasons, researchers are developing types reactions and applications processes. These bond can be divided into two general classes: those directed coordination an existing functional group prior cleavage (directed) occurring without (undirected). undirected much less common challenging develop than reactions. This outlook will focus on functionalization, as well related that occur noncovalent association catalyst cleavage. inherent challenges conducting methods for being developed presented, along with factors govern selectivity in Finally, this discusses future directions research emphasis limitations must overcome if type methodology is become widely used academia industry.

Language: Английский

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Catalytic Silylation of Unactivated C–H Bonds

Chemical Reviews, Journal Year: 2015, Volume and Issue: 115(17), P. 8946 - 8975

Published: Feb. 25, 2015

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTCatalytic Silylation of Unactivated C–H BondsChen Cheng and John F. Hartwig*View Author Information Department Chemistry, University California, Berkeley, California 94720, United States*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 17, 8946–8975Publication Date (Web):February 25, 2015Publication History Received10 November 2014Published online25 February 2015Published inissue 9 September 2015https://pubs.acs.org/doi/10.1021/cr5006414https://doi.org/10.1021/cr5006414review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views24505Altmetric-Citations556LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated to reflect usage leading up last few days.Citations number other articles citing this article, calculated by Crossref daily. Find more information about citation counts.The Altmetric Attention Score is 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 Other access optionsGet e-Alertsclose SUBJECTS:Catalysts,Chemical reactions,Group 14 compounds,Hydrocarbons,Silylation Get e-Alerts

Language: Английский

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Manganese-Catalyzed C–H Activation

ACS Catalysis, Journal Year: 2016, Volume and Issue: 6(6), P. 3743 - 3752

Published: April 27, 2016

Manganese is found in the active center of numerous enzymes that operate by an outer-sphere homolytic C–H cleavage. Thus, a plethora bioinspired radical-based functionalizations manganese catalysis have been devised during past decades. In contrast, organometallic activation means has emerged only recently as increasingly viable tool organic synthesis. These manganese(I)-catalyzed processes enabled variety with ample scope, which very set stage for substitutive functionalizations. The versatile largely operates isohypsic, thus redox-neutral, mode action through chelation assistance, and provided step-economical access to structurally divers compounds relevance inter alia bioorganic, agrochemical, medicinal chemistry well material sciences.

Language: Английский

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Transition metal-catalyzed ketone-directed or mediated C–H functionalization

Chemical Society Reviews, Journal Year: 2015, Volume and Issue: 44(21), P. 7764 - 7786

Published: Jan. 1, 2015

Transition metal-catalyzed C-H functionalization has evolved into a prominent and indispensable tool in organic synthesis. While nitrogen, phosphorus sulfur-based functional groups (FGs) are widely employed as effective directing (DGs) to control the site-selectivity of activation, use common FGs (e.g. ketone, alcohol amine) DGs been continuously pursued. Ketones an especially attractive choice substrates due their prevalence various molecules versatile reactivity synthetic intermediates. Over last two decades, transition that is directed or mediated by ketones experienced vigorous growth. This review summarizes these advancements three major categories: ketone carbonyls DGs, direct β-functionalization, α-alkylation/alkenylation with unactivated olefins alkynes. Each subsections discussed from perspective strategic design reaction discovery.

Language: Английский

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Transition metal-catalyzed site- and regio-divergent C–H bond functionalization

Chemical Society Reviews, Journal Year: 2017, Volume and Issue: 46(14), P. 4299 - 4328

Published: Jan. 1, 2017

The regioselectivity of C–H functionalization reactions can be redirected to obtain regioisomeric products form the same starting materials.

Language: Английский

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

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(24), P. 14957 - 15074

Published: Oct. 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.

Language: Английский

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N-Acyl Amino Acid Ligands for Ruthenium(II)-Catalyzed meta-C–H tert-Alkylation with Removable Auxiliaries

Journal of the American Chemical Society, Journal Year: 2015, Volume and Issue: 137(43), P. 13894 - 13901

Published: Sept. 29, 2015

Acylated amino acid ligands enabled ruthenium(II)-catalyzed C-H functionalizations with excellent levels of meta-selectivity. The outstanding catalytic activity the ruthenium(II) complexes derived from monoprotected acids (MPAA) set stage for first ruthenium-catalyzed meta-functionalizations removable directing groups. Thereby, meta-alkylated anilines could be accessed, which are difficult to prepare by other means direct aniline functionalizations. robust nature versatile ruthenium(II)-MPAA was reflected challenging remote transformations tertiary alkyl halides on derivatives as well pyridyl-, pyrimidyl-, and pyrazolyl-substituted arenes. Detailed mechanistic studies provided strong support an initial reversible ruthenation, followed a SET-type C-Hal activation through homolytic bond cleavage. Kinetic analyses confirmed this hypothesis unusual second-order dependence reaction rate ruthenium catalyst concentration. Overall, report highlights exceptional acylated acids, should prove instrumental chemistry beyond functionalization.

Language: Английский

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