Iron Catalysis in Organic Synthesis

Chemical Reviews, Год журнала: 2015, Номер 115(9), С. 3170 - 3387

Опубликована: Март 9, 2015

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTIron Catalysis in Organic SynthesisIngmar Bauer and Hans-Joachim Knölker*View Author Information Department Chemie, Technische Universität Dresden, Bergstraße 66, 01069 Germany*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 9, 3170–3387Publication Date (Web):March 2015Publication History Received5 August 2014Published online9 March 2015Published inissue 13 May 2015https://pubs.acs.org/doi/10.1021/cr500425uhttps://doi.org/10.1021/cr500425ureview-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views52105Altmetric-Citations1500LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 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:Anions,Catalysts,Chemical reactions,Hydrocarbons,Reagents Get e-Alerts

Язык: Английский

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Catalysis of Radical Reactions: A Radical Chemistry Perspective

Angewandte Chemie International Edition, Год журнала: 2015, Номер 55(1), С. 58 - 102

Опубликована: Окт. 13, 2015

Abstract The area of catalysis radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most innate chains which form products without any catalyst. How do we know if a species added “catalytic amounts” is catalyst, an initiator, or something else? Herein critically address both catalyst‐free through the lens chemistry. Basic principles kinetics thermodynamics are used problems initiation, propagation, inhibition chains. differs other areas catalysis. Whereas efficient chain difficult catalyze because individual steps fast, inefficient processes non‐chain afford diverse opportunities for catalysis, illustrated with selected examples.

Язык: Английский

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Oxidative C–H/C–H Coupling Reactions between Two (Hetero)arenes

Chemical Reviews, Год журнала: 2017, Номер 117(13), С. 8787 - 8863

Опубликована: Янв. 13, 2017

Transition metal-mediated C-H bond activation and functionalization represent one of the most straightforward powerful tools in modern organic synthetic chemistry. Bi(hetero)aryls are privileged π-conjugated structural cores biologically active molecules, functional materials, ligands, intermediates. The oxidative C-H/C-H coupling reactions between two (hetero)arenes through 2-fold offer a valuable opportunity for rapid assembly diverse bi(hetero)aryls further exploitation their applications pharmaceutical material sciences. This review provides comprehensive overview fundamentals transition metal-mediated/catalyzed (hetero)arenes. substrate scope, limitation, reaction mechanism, regioselectivity, chemoselectivity, as well related control strategies these discussed. Additionally, established methods synthesis natural products new materials exemplified. In last section, short introduction on oxidant- or Lewis acid-mediated Ar-H/Ar-H is presented, considering that it very method construction biaryl units polycylic arenes.

Язык: Английский

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Organocatalysis in Inert C–H Bond Functionalization

Chemical Reviews, Год журнала: 2017, Номер 117(13), С. 9433 - 9520

Опубликована: Фев. 13, 2017

As two coexisting and fast-growing research fields in modern synthetic chemistry, the merging of organocatalysis C–H bond functionalization is well foreseeable, joint force along this line has been demonstrated to be a powerful approach making inert more viable, predictable, selective. In review, we provide comprehensive summary over past decades. The review arranged by types bonds including alkane C–H, arene vinyl as those activated benzylic allylic alpha heteroatom such nitrogen oxygen. each section, discussion classified explicit organocatalytic mode involved.

Язык: Английский

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Katalyse von Radikalreaktionen: Konzepte aus Sicht der Radikalchemie

Angewandte Chemie, Год журнала: 2015, Номер 128(1), С. 58 - 106

Опубликована: Окт. 13, 2015

Abstract Das Gebiet der Katalyse von Radikalreaktionen erfuhr in jüngster Zeit höchste Aufmerksamkeit. Viele interessante wurden entdeckt und dann über Katalysezyklen erklärt. Diese Zyklen stellen allerdings selten den einzigen Weg vom Substrat zum Produkt dar. Die meisten weisen intrinsische Ketten auf, die das Potential haben, auch ohne Katalysator zu bilden. Wie wissen wir nun, ob eine “katalytischen Mengen” zugegebene Verbindung einen Katalysator, Initiator oder gar etwas anderes darstellt? Im vorliegenden Aufsatz besprechen kritisch sowohl Katalysator‐freie als katalytische aus Sicht Radikalchemie. Grundlagen Kinetik Thermodynamik werden genutzt, um Probleme Initiierung, Propagation Inhibierung adressieren. unterscheidet sich anderen Gebieten mehreren Aspekten. Wohingegen Kettenreaktionen schwierig katalysieren sind, da zugrundeliegenden individuellen Schritte so schnell ablaufen, bieten ineffiziente Kettenprozesse nicht‐Kettenprozesse verschiedene Möglichkeiten Katalyse. Wir illustrieren Konzepte mit ausgewählten Beispielen klassischen, aber jüngsten Literatur.

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Simple and Clean Photoinduced Aromatic Trifluoromethylation Reaction

Journal of the American Chemical Society, Год журнала: 2016, Номер 138(18), С. 5809 - 5812

Опубликована: Май 3, 2016

We describe a simple, metal- and oxidant-free photochemical strategy for the direct trifluoromethylation of unactivated arenes heteroarenes under either ultraviolet or visible light irradiation. demonstrated that photoexcited aliphatic ketones, such as acetone diacetyl, can be used promising low-cost radical initiators to generate CF3 radicals from sodium triflinate efficiently. The broad utility this its benefit medicinal chemistry are by unprotected bidentate chelating ligand, xanthine alkaloids, nucleosides, related antiviral drug molecules.

Язык: Английский

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Recent Development of Aryl Diazonium Chemistry for the Derivatization of Aromatic Compounds

Chemical Reviews, Год журнала: 2021, Номер 121(10), С. 5741 - 5829

Опубликована: Апрель 9, 2021

Aryl diazonium salts are versatile building blocks in organic synthesis. In light of the ever-increasing importance aryl spanning most disciplines chemical sciences, we review recent development chemistry over past seven years (2013-2020). Special emphasis is put on various new transformations involving generation radical intermediates via thermal, photochemical, and electrochemical means. Recent advances transition metal-catalyzed reactions using also reviewed. Together, these newly developed significantly expand synthetic chemist's repertoire aromatic carbon-carbon carbon-heteroatom bond forming methods precursors, providing powerful tools for synthesis modification complex molecular scaffolds.

Язык: Английский

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Radical Retrosynthesis

Accounts of Chemical Research, Год журнала: 2018, Номер 51(8), С. 1807 - 1817

Опубликована: Авг. 2, 2018

ConspectusIn The Logic of Chemical Synthesis, E. J. Corey stated that the key to retrosynthetic analysis was a "wise choice appropriate simplifying transforms" (Corey, J.; Cheng, X.-M. Synthesis; John Wiley: New York, 1989). Through lens "ideality", chemists can identify opportunities lead more practical, scalable, and sustainable synthesis. percent ideality synthesis is defined as [(no. construction rxns) + (no. strategic redox rxns)]/(total no. steps) × 100. A direct consequence designing "wise" or "ideal" plans new transformations often need invention. For example, if functional group interconversions are be avoided, one faced with prospect directly functionalizing C–H bonds (Gutekunst, W. R.; Baran, P. S. Chem. Soc. Rev. 2011, 40, 1976; Brückl, T.; et al. Acc. Res. 2012, 45, 826). If protecting groups minimized, methods testing limits chemoselectivity require invention (Baran, S.; Nature 2007, 446, 404; Young, I. Nat. 2009, 1, 193). Finally, extraneous manipulations eliminated, generating skeletal result (Burns, N. Z.; Angew. Chem., Int. Ed. 48, 2854). Such analyses applied total have seen an explosion interest in recent years. Thus, it interplay aspirational demands available influence inspire ingenuity. Corey's sage advice holds true when endeavoring complex molecule synthesis, but together tenets avoiding concession steps leads most strategically tactically optimal route (Hendrickson, B. Am. 1975, 97, 5784; Gaich, Org. 2010, 75, 4657).Polar disconnections intuitive underlie much logic. Undergraduates exposed multistep taught assemble organic molecules through combination positively negatively charged synthons because, after all, opposites attract. Indeed, employed two-electron C–C bond forming reactions today those based upon either classical cross-coupling (e.g., Suzuki, Negishi, Heck) polar additions (aldol, Michael, Grignard). These mainstay modern revolutionized way constructed due their robust predictable nature. In contrast, radical chemistry sparsely covered beyond basic principles chain processes (i.e., halogenation). historical perception radicals somewhat uncontrollable species does not help situation. As result, synthetic prone make radical-based during first-pass analyses.Recent use one-electron (RCC) has been fueled by realization uniquely chemoselective profiles they uncover for dramatically general, such couplings proceed relying on innate preferences substrate (innate RCC) interception mediator (usually transition metal) achieve programmed RCC. This Account presents series case studies illustrating inherent tactical advantages employing both types cross-couplings variety disparate settings. Thematically, clear disconnections, while considered intuitive, serve enable syntheses feature minimal chemistry, interconversions, nonstrategic fluctuations.

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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Functionalization of Pyrene To Prepare Luminescent Materials—Typical Examples of Synthetic Methodology

Chemistry - A European Journal, Год журнала: 2016, Номер 22(34), С. 11898 - 11916

Опубликована: Июль 8, 2016

Abstract Pyrene‐based π‐conjugated materials are considered to be an ideal organic electro‐luminescence material for application in semiconductor devices, such as light‐emitting diodes (OLEDs), field‐effect transistors (OFETs) and photovoltaics (OPVs), so forth. However, the great drawback of employing pyrene luminescence is formation excimer emission, which quenches efficiency at high concentration or solid‐state. Thus, order obtain highly efficient optical scientists have devoted much effort tuning structure derivatives realize exploitable properties by two strategies, 1) introducing a variety moieties core, 2) exploring effective convenient synthetic strategies functionalize core. Over past decades, our group has mainly focused on methodologies functionalization core; we found that formylation/acetylation bromination can selectly lead K‐region Lewis acid catalysis. Herein, this Minireview highlights direct approaches (such formylation, bromination, oxidation, de‐ tert ‐butylation reactions, etc.) advance research luminescent electronic applications. Further, article demonstrates future direction chemistry asymmetric applications some classical pyrenes, well latest breakthroughs. In addition, photophysical pyrene‐based molecules briefly reviewed. To give current overview development chemistry, review selectively covers reports concepts from period covering late 2011 present day.

Язык: Английский

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