The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c01332. Find more information about Crossref citation counts. concerted proton-electron transfer (CPET) concerted electron-proton transfer (CEP) electron transfer proton transfer (ETPT) electron-proton transfer (EPT) Termiology 7 The term PCET has come to be used more broadly … You’ve supercharged your research process with ACS and Mendeley! https://pubs.acs.org/doi/abs/10.1021/ja5056774, 2. Catalytic C–N Bond-Forming Reactions Enabled by Proton-Coupled Electron Transfer Activation of Amide N–H Bonds, Catalytic C–N Bond-Forming Reactions Enabled by Proton-Coupled Electron Transfer Activation of Amide N–H Bonds, ACS Catal. Chem. These reactions occur at room temperature under visible light irradiation and are jointly catalyzed by an iridium(III) photocatalyst, a dialkyl phosphate base, and a thiol hydrogen atom donor. Chem. https://pubs.acs.org/doi/abs/10.1021/ja404342j, © 2020 The Trustees of Princeton University, 11712–11738.

Studies outlining the synthetic scope (>60 examples) and mechanistic features of the reaction are presented. A battery of kinetic, electrochemical, and spectroscopic studies of this process indicates a radical chain mechanism of dehydrogenation involving selective HAT from the substrate by an alkoxy radicals. Should celecoxib be contraindicated in patients who are allergic to sulfonamides? DOI: 10.1021/ja4100595. Copyright © 2019 American Academy of Allergy, Asthma & Immunology. The Knowles lab has demonstrated that it is possible to achieve such a transformation with high enantioselectivity by using a chiral phosphate base to activate the N–H bond of a sulfonamide and form a chiral ion pair capable of undergoing enantioselective PCET. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. LES SULFAMIDES ANTIBACTERIENS . Abstract: A new catalytic method is described to access carbocation intermediates via the mesolytic cleavage of alkoxyamine radical cations. Visible-Light-Enabled Ortho-Selective Aminopyridylation of Alkenes with N-Aminopyridinium Ylides. Abstract: While olefin amination with aminium radical cations is a classical method for C–N bond formation, catalytic variants that utilize simple 2° amine precursors remain largely undeveloped. Please enable it to take advantage of the complete set of features! The term PCET was used to distinguish it from sequential ET-PT or PT-ET, and H-Atom Transfer Proposed Mechanisms (pH 2-9) proton transfer is coupled with electron transfer. These reactions are redox-neutral and completely atom-economical, exhibit broad functional group tolerance, and occur readily at room temperature under visible light irradiation. Soc. 2014, 20, 2819–2826. Synthesis of β‐Diamine Building Blocks by Photocatalytic Hydroamination of Enecarbamates with Amines, Ammonia and N−H Heterocycles. DOI: 10.1021/jacs.5b03428. 2016, 6, 2894–2903. Abstract: Here we report a ternary catalyst system for the intramolecular hydroamidation of unactivated olefins using simple N-aryl amide derivatives. Ces deux séries de produits ont reçu des applications pharmaceutiques de tout premier ordre, notamment dans plusieurs dom NLM Enantioselective Photoredox Catalysis Enabled by Proton-Coupled Electron Transfer: Development of an Asymmetric Aza-Pinacol Cyclization, Lydia J. Rono, Hatice G. Yayla, David Y. Wang, Michael F. Armstrong, Robert R. Knowles, Enantioselective Photoredox Catalysis Enabled by Proton-Coupled Electron Transfer: Development of an Asymmetric Aza-Pinacol Cyclization, J. These reactions occur at room temperature under visible light irradiation and are jointly catalyzed by an iridium(III) photocatalyst, a dialkyl phosphate base, and a thiol hydrogen atom donor. without permission from the American Chemical Society. Taken together with a unique kinetic feature of concerted PCET, this remarkable energetic range presents a framework to develop methods for the direct homolytic activation of many otherwise energetically inaccessible organic functional groups under unusually mild, catalytic conditions.
https://pubs.acs.org/doi/abs/10.1021/ja4100595, 1. Find more information on the Altmetric Attention Score and how the score is calculated. the Altmetric Attention Score and how the score is calculated. Chem. Abstract: Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen–hydrogen (N–H) bonds of N-alkyl amides.

These reactions are proposed to proceed via N-centered radicals formed by proton-coupled electron transfer (PCET) activation of sulfonamide N–H bonds. Delayed skin testing including patch tests to sulfonamides is rarely positive. https://pubs.acs.org/doi/abs/10.1021/acs.accounts.6b00272, 12. Please use this identifier to cite or link to this item: Department of Slavic Languages and Literatures, Lewis-Sigler Institute for Integrative Genomics, Liechtenstein Institute on Self-Determination, Princeton School of Public and International Affairs, Princeton University Doctoral Dissertations, 2011-2020, Princeton University Undergraduate Senior Theses, 1924-2020, http://arks.princeton.edu/ark:/88435/dsp015h73pz872, Towards Understanding the Mechanism of Intermolecular anti-Markovnikov Hydroamination of Unactivated Alkenes with Sulfonamides. An enantioselective, radical-based method for the intramolecular hydroamination of alkenes with sulfonamides is reported. PCET typically occurs through a hydrogen-bond complex between the substrate and a proton donor/acceptor. Sci. Here we report a catalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated alkenes using primary and secondary sulfonamides. Abstract: Here we describe a dual catalyst system comprised of an iridium photocatalyst and weak phosphate base that is capable of both selectively homolyzing the N–H bonds of N-arylamides (bond dissociation free energies ~ 100 kcal/mol) via concerted proton-coupled electron transfer (PCET) and mediating efficient carboamination reactions of the resulting amidyl radicals. Although immediate skin testing can be performed in patients with histories of immediate reactions, they are infrequently positive and wane over time. Khan DA(1), Knowles SR(2), Shear NH(3). These reactions occur at room temperature under visible light irradiation and are jointly catalyzed by an iridium(III) photocatalyst, a dialkyl phosphate base, and a thiol hydrogen atom donor. 2018, 140, 741–747. In the latter process—a subset of the classical Hofmann–Löffler–Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C–H bonds. We successfully identified compatible combinations of one-electron oxidants and Brønsted bases that, although unable to activate the amide substrates independently, act concomitantly with the requisite energetics to selectively homolyze the N–H bond via concerted PCET. Clipboard, Search History, and several other advanced features are temporarily unavailable. Files available from the ACS website may be downloaded for personal use only. 2013, 135, 10022–10025.

Martin P. Rauch, Robert R. Knowles: https://www.ingentaconnect.com/content/scs/chimia/2018/00000072/f0020007/art00006, Emily C. Gentry, Robert R. Knowles: https://pubs.acs.org/doi/abs/10.1021/acs.accounts.6b00272, Kyle T. Tarantino, David C. Miller, Ted A. Callon, Robert R. Knowles: https://pubs.acs.org/doi/abs/10.1021/jacs.5b03428, Andrew J. Musacchio, Brendan C. Lainhart, Xin Zhang, Saeed G. Naguib, Trevor C. Sherwood, Robert R. Knowles: https://science.sciencemag.org/content/355/6326/727, © 2020 The Trustees of Princeton University. National Center for Biotechnology Information, Unable to load your collection due to an error, Unable to load your delegates due to an error. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon–carbon (C–C) bonds. DOI: 10.1007/s41061-016-0030-6. In this Account, we highlight two recent examples from our group outlining the use of concerted PCET as a platform for the development of catalytic and enantioselective reactions of neutral ketyl radicals. This work seeks to provide insight on the interactions between the sulfonamide, chiral phosphate base, and Iridium photocatalyst during the course of the catalytic cycle.

This C–H alkylation represents a catalytic variant of the Hofmann–Löffler–Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C–C bonds. HHS Compte tenu de l'important développement des résistances acquises, les indications des sulfamides ou du TMP doivent quasiment toutes disparaître qu'il s'agisse du sulfaméthizol (RufolÒ) ou du TMP (WellcoprimÒ) dans les infections urinaires ou qu'il s'agisse de l'association sulfafurazole-érythromycine (PédiazoleÒ) dans les otites de l'enfant.


Non-covalent interactions between the neutral sulfonamidyl radical and a chiral phosphoric acid generated in the PCET event are hypothesized to serve as the basis for asymmetric induction in a subsequent C–N bond forming step, achieving selectivities of up to 98:2 er. PCET typically occurs through a hydrogen-bond complex between the substrate and a proton donor/acceptor.

Sulfonamide antimicrobials are commonly reported as causing drug allergy and have been implicated in a variety of hypersensitivity reactions including immediate IgE-mediated reactions, benign T-cell-mediated rashes, and severe cutaneous adverse reactions such as Stevens-Johnson syndrome, toxic epidermal necrolysis, and drug reaction with eosinophilia and systemic symptoms. 2016, 49, 1546–1556. Among the primary goals of this work is to establish concerted PCET as a general mechanism for homolytic bond activation that is complementary to and broader in scope than conventional hydrogen atom transfer (HAT) chemistry. Find NCBI SARS-CoV-2 literature, sequence, and clinical content: https://www.ncbi.nlm.nih.gov/sars-cov-2/. as well as a reactive carbocation intermediate that can be intercepted by a wide range of nucleophiles. USA.gov. A series of H-atom, electron, and proton transfer events with a thiophenol cocatalyst furnish the product and regenerate the active forms of the photocatalyst and base. Electronic address: dave.khan@utsouthwestern.edu. https://pubs.acs.org/doi/full/10.1021/jacs.5b09671, 7. Soc. DOI: 10.1021/acscatal.6b00486. DOI: 10.1021/acs.accounts.6b00272. DOI: 10.1021/acs.accounts.6b00272. 2016, 374, 30. Abstract: Olefin aminations are important synthetic technologies for the construction of aliphatic C–N bonds.

Soc.

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