DOCSLIB.ORG

Activation, Deactivation and Reversibility Phenomena in Homogeneous Catalysis: a Showcase Based on the Chemistry of † Rhodium/Phosphine Catalysts

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Activation, Deactivation and Reversibility Phenomena in Homogeneous Catalysis: a Showcase Based on the Chemistry of † Rhodium/Phosphine Catalysts catalysts Review Activation, Deactivation and Reversibility Phenomena in Homogeneous Catalysis: A Showcase Based on the Chemistry of y Rhodium/Phosphine Catalysts Elisabetta Alberico 1 , Saskia Möller 2, Moritz Horstmann 2, Hans-Joachim Drexler 2 and Detlef Heller 2,* 1 Istituto di Chimica Biomolecolare—CNR, Tr. La Crucca 3, 07100 Sassari, Italy 2 Leibniz-Institut für Katalyse e.V., Albert-Einstein-Strasse 29a, 18059 Rostock, Germany * Correspondence: [email protected] Dedicated to Piet W. N. M. van Leeuwen. y Received: 5 June 2019; Accepted: 29 June 2019; Published: 30 June 2019 Abstract: In the present work, the rich chemistry of rhodium/phosphine complexes, which are applied as homogeneous catalysts to promote a wide range of chemical transformations, has been used to showcase how the in situ generation of precatalysts, the conversion of precatalysts into the actually active species, as well as the reaction of the catalyst itself with other components in the reaction medium (substrates, solvents, additives) can lead to a number of deactivation phenomena and thus impact the efficiency of a catalytic process. Such phenomena may go unnoticed or may be overlooked, thus preventing the full understanding of the catalytic process which is a prerequisite for its optimization. Based on recent findings both from others and the authors’ laboratory concerning the chemistry of rhodium/diphosphine complexes, some guidelines are provided for the optimal generation of the catalytic active species from a suitable rhodium precursor and the diphosphine of interest; for the choice of the best solvent to prevent aggregation of coordinatively unsaturated metal fragments and sequestration of the active metal through too strong metal–solvent interactions; for preventing catalyst poisoning due to irreversible reaction with the product of the catalytic process or impurities present in the substrate. Keywords: Rh; homogeneous catalysis; catalyst deactivation 1. Introduction The term “catalysis” was first introduced by the Swedish chemist Jöns Jacob Berzelius in a report published in 1835 by the Swedish Academy of Sciences [1]. The report was a reflection on earlier findings by European scientists on chemical changes both in homogeneous and heterogeneous systems. Although far from being understood, the recorded phenomena were unified, according to Berzelius, by the fact that “several simple or compound bodies, soluble and insoluble, have the property of exercising on other bodies an action very different from chemical affinity. By means of this action they produce, in these bodies, decompositions of their elements and different recombinations of these same elements to which they remain indifferent.” [2] Berzelius designated this unifying property as “catalytic force” and coined the term “catalysis” to describe the decomposition of bodies by this force. Catalysis is the macroscopic manifestation of the reduction of the activation energy of an exergonic reaction. It is as such a purely kinetic phenomenon; Berzelius however did not know the concept of reaction rate yet and therefore he could only describe known findings phenomenologically. Catalysts 2019, 9, 582; doi:10.3390/catal9070582 www.mdpi.com/journal/catalysts Catalysts 2019, 9, 582 2 of 45 Catalysts 2018, 8, x FOR PEER REVIEW 2 of 45 Catalysts 2018, 8, x FOR PEER REVIEW 2 of 45 It was not until 1894 that Wilhelm Ostwald succeeded in giving an exact description of catalysis [3]. Later,It was in notnot his untiluntil Nobel 18941894 Lecture that that Wilhelm Wilhelm of 1909, Ostwald Ostwaldhe said succeededabout succeeded catalysis in in giving giving that an“… an exact the exact essence description description of which of catalysisof catalysisis not [to3]. be[3].Later, sought Later, in his inin Nobel histhe Nobelpromotion Lecture Lecture of of 1909, aof reaction, 1909, he said he but said about in about its catalysis acceleration,…” catalysis that that “ ::: “… [4]the theFurther essence essence introduction of whichof which is not isinto not to the beto historybesought sought of in catalysis thein the promotion promotion can be offound aof reaction, a reaction,in references but but in in its[5–8]. its acceleration, acceleration,…” ::: ”[ [4]4] FurtherFurther introductionintroduction into the history of catalysis can be found in references [[5–8].5–8]. An updated definition to be found in the IUPAC Compendium of Chemical Terminology, though,An suggestsupdated adefinition clear distinction to be foundbetween in athe catalyst, IUPAC that Compendium is a substance of that Chemical increases Terminology, the rate of a An updated definition to be found in the IUPAC Compendium of Chemical Terminology, though, reaction,though, suggests and an inhibitor, a clear distinction which instead between reduces a catalyst, it [9]. that is a substance that increases the rate of a suggests a clear distinction between a catalyst, that is a substance that increases the rate of a reaction, reaction,Catalysis and an is inhibitor,widely applied which insteadboth in reducesindustry it [9].[10–13] and academia [14,15]: the switch from a and an inhibitor, which instead reduces it [9]. stoichiometricCatalysis processis widely to applieda catalytic both one in represents industry a[10–13] way to andgreatly academia improve [14,15]: efficiency, the switch as less energyfrom a Catalysis is widely applied both in industry [10–13] and academia [14,15]: the switch from a inputstoichiometric and less process feedstock to a catalyticare usually one representsrequired, lea ssway waste to greatly is generated, improve efficiency,and a greater as less product energy stoichiometric process to a catalytic one represents a way to greatly improve efficiency, as less energy selectivityinput and isless in generalfeedstock achieved. are usually required, less waste is generated, and a greater product input and less feedstock are usually required, less waste is generated, and a greater product selectivity selectivityAlthough is in heterogeneousgeneral achieved. catalysts were the first to be applied at the industrial level, where they is in general achieved. dominatedAlthough the heterogeneousscene for several catalysts decades, were homogenous the first to catalystsbe applied started at the toindustrial raise increasing level, where attention they Although heterogeneous catalysts were the first to be applied at the industrial level, where they indominated the early the1960s scene when for theyseveral were decades, considered homogenous for the large catalysts scale startedproduction to raise of bulkincreasing chemicals. attention One dominated the scene for several decades, homogenous catalysts started to raise increasing attention majorin the contributionearly 1960s when came theyin those were years considered from Slaugh for th ande large coworkers scale production at Shell Research of bulk (USA)chemicals. [16] laterOne in the early 1960s when they were considered for the large scale production of bulk chemicals. One onmajor supported contribution by further came in developments those years from in Wilkinson’sSlaugh and coworkerslaboratory at [17], Shell of Research Co- and (USA) Rh-phosphine [16] later major contribution came in those years from Slaugh and coworkers at Shell Research (USA) [16] catalystson supported which by furtherwere applied developments in the in rapid,Wilkinson’s selective laboratory liquid-phase [17], of hydroformylationCo- and Rh-phosphine and later on supported by further developments in Wilkinson’s laboratory [17], of Co- and Rh-phosphine hydrogenationcatalysts which of alkeneswere applied under mildin conditions.the rapid, Theselective possibility liquid-phase to tailor the hydroformylation catalyst properties and by catalysts which were applied in the rapid, selective liquid-phase hydroformylation and hydrogenation properhydrogenation selection of of alkenes additional under ligands mild triggeredconditions. further The possibility research which to tailor led the in thecatalyst following properties decades by of alkenes under mild conditions. The possibility to tailor the catalyst properties by proper selection of toproper the development selection of additionalof important ligands industrial triggered processe furthers based research on the which use of ledhomogeneous in the following catalysts decades such additional ligands triggered further research which led in the following decades to the development of asto thethe development SHOP process of important for the oligomerization industrial processe of sethylene based on or the the use producti of homogeneouson of enantioenriched catalysts such important industrial processes based on the use of homogeneous catalysts such as the SHOP process herbicideas the SHOP Metholachlor process forand the the oligomerizationaroma ingredient of citronellal ethylene [11].or the production of enantioenriched herbicide Metholachlor and the aroma ingredient citronellal [11]. Catalysts 2019, 9, 582 3 of 45 for the oligomerization of ethylene or the production of enantioenriched herbicide Metholachlor and the aroma ingredient citronellal [11]. The discovery of a novel catalyst for a certain process may be serendipitous or the result of extensive screening. Yet improvement of the catalyst productivity and efficiency, both in terms of activity and selectivity in the desired product, requires knowledge of the chemical transformations the catalyst undergoes during the course of the reaction. The nature and distribution of the resulting species may vary over time due to the interaction
Load more

Recommended publications
  • Design and Synthesis of Chiral Ligands and Their Applications in Transition
    The Pennsylvania State University The Graduate School Department of Chemistry DESIGN AND SYNTHESIS OF CHIRAL LIGANDS AND THEIR APPLICATIONS IN TRANSITION METAL-CATALYZED ASYMMETRIC REACTIONS A Dissertation in Chemistry by Wei Li 2012 Wei Li Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy May 2012 The dissertation of Wei Li was reviewed and approved* by the following: Gong Chen Assistant Professor of Chemistry Dissertation Advisor Chair of Committee Tom Mallouk Evan Pugh Professor of Material Chemistry and Physics Alex Radosevich Assistant Professor of Chemistry Qing Wang Associate Professor of Material Science and Engineering Xumu Zhang Professor of Chemistry Special Member Barbara J. Garrison Shapiro Professor of Chemistry Head of the Department of Chemistry *Signatures are on file in the Graduate School iii ABSTRACT Transition metal catalyzed reactions are among the most powerful and direct approaches for the synthesis of organic molecules. During the past several decades, phosphorous-containing ligands have been extensively studied in transition metal - catalyzed transformations particularly asymmetric hydrogenations. Development of new chiral ligands and efficient catalyst systems for various prochiral unsaturated substrates in asymmetric hydrogenations are the focus of this dissertation. An important family of atropisomeric biaryl bisphosphine ligands, C3*-TunePhos and related bisaminophosphines have been designed and synthesized. The Ru catalysts of the highly modular C3*-TunePhos have been proved to be highly efficient (up to 99.8% ee, up to 1,000,000 TON) for practical asymmetric hydrogenations of a wide range of unfunctionalized ketones as well as α-, β- keto esters and N-2-substituted allylphthalimides. The synthetic utility of bisaminophosphine ligands was studied for rhodium-catalyzed asymmetric hydrogenations of α-dehydroamino acid esters, affording up to 98% ee’s.
    [Show full text]
  • Synthesis of Iron Carbonyl Complexes 64
    FAKULTÄT FÜR CHEMIE Lehrstuhl für Strukturanalytik in der Katalyse The Synthesis, Characterization and Performance of Well-Defined Iron Carbonyl Catalysts Hüseyin Güler Vollständiger Abdruck der von der Fakultät für Chemie der Technischen Universität München zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften genehmigten Dissertation. Vorsitzender : Univ.-Prof. Dr. Klaus Köhler Prüfer der Dissertation: 1. Prof. Moniek Tromp, Ph.D. Univ. Amsterdam / Niederlande 2. Univ.-Prof. Dr. Thomas Brück Die Dissertation wurde am 28.05.2015 bei der Technischen Universität München eingereicht und durch die Fakultät für Chemie am 28.07.2015 angenommen. i THE SYNTHESIS, CHARACTERIZATION AND PERFORMANCE OF WELL-DEFINED IRON CARBONYL CATALYSTS HUSEYIN GULER Doctoral Thesis Technische Universität München May 2015 ii Hüseyin Güler: The Synthesis, Characterization and Performance of Well-Defined Iron Carbonyl Catalysts. © May 2015 iii ABSTRACT The synthesis of well-defined, uniform iron carbonyl based complexes incorporating disphoshine ligands was performed and their performance as homogeneous catalysts evaluated. The iron carbonyl diphosphine complexes were formed by reaction of Fe3(CO)12 and bidentate diphosphine ligands. Detailed characterizations as well as kinetic studies were performed to provide fundamental insights in the catalyst properties. These iron carbonyl complexes were examined as homogeneous catalysts in 2-propanol-based transfer hydrogenation of ketone. The influence of different reaction parameters on the catalytic performance was investigated. The scope and limitations of the described catalyst for the reduction of a series different ketones was shown. In most cases, high conversion and selectivity are obtained. Mechanistic and kinetic studies indicate a monohydride reaction pathway for the homogeneous iron catalyst. Iron carbonyls supported on γ-Al2O3 were obtained and their performance as heterogeneous catalysts evaluated.
    [Show full text]
  • Chemfile Vol.6 No 8
    2006 VOLUME 6 NUMBER 8 Privileged Ligands DUPHOS AND BPE PHOSPHOLANE LIGANDS DSM MONOPHOS™ FAMILY CHIRALQUEST PHOSPHINE LIGANDS SOLVIAS® FERROLceNYL-BASed LIGANDS (S)-MonoPhosTM: a powerful ligand for asymmetric synthesis. sigma-aldrich.com Introduction Chemists are continually searching for novel, efficient chiral transition metal catalysts to effect ever more difficult transformations. Highly effective asymmetric catalytic systems Vol. 6 No. 8 offer the possibility of synthesizing either desired enantiomer pure from simple achiral Aldrich Chemical Co., Inc. starting materials, with the chiral products then being directly employed in natural 1 Sigma-Aldrich Corporation product synthesis. Research groups have spent much well-earned effort in designing 6000 N. Teutonia Ave. high performance ligand platforms2 that exhibit the following general characteristics: Milwaukee, WI 53209, USA 1) the synthesis should be economically viable and allow for systematic variations in the architecture; 2) most (if not all) members of the ligand family should be readily produced from milligram to kilogram scale; and 3) the ligands should bind strongly to the metal center as well as generate a highly active and selective catalyst system. To Place Orders Chiral salens,3 bisoxazolines,4 tartrate ligands,5 and cinchona alkaloids6 represent the Telephone 800-325-3010 (USA) original “privileged ligands” classes that effect a wide variety of transformations under FAX 800-325-5052 (USA) exceptional enantiocontrol and with high productivity. Impressively, R&D groups
    [Show full text]
  • Ligand 960 Accessible Molecular Surfa
    1699 Index a acrylate 199, 1612 abiraterone 426 – derivatives 1115, 1117 abnormal lactone (AL) 1495, 1496 – esters, synthesis of 1610 π-acceptors 828 acrylic acid 126, 1612 – π*-acceptor 810 – based on CO2 1610 – ligand 960 – thermodynamic situation 1611 accessible molecular surface (AMS) 834 acrylonitrile-butadiene-polystyrene acenaphthene imine derivative ligands 257 microencapsulated Os 1514 acetaldehyde 508 actinides 1071 – from ethylene 500 activated carbon 1343 – oxidation 95 activation energy 963 acetamide, transamidation of activation reaction 233 – amino acid catalyzed 1436 active catalyst system 283 acetic acid 93, 709, 1526 active noble metal complexes, reoxidation – nickel-based catalysts 105 1264 acetic anhydride 110, 111 acyclic diene metathesis polymerization 2´-acetonaphthone 735 (ADMET) 824 acetonitrile 708, 1547 acyclic ketones, BV oxidation of 1502 acetophenones 726, 730, 732, 734, 738, 1047 acyclic precursors 1343 – derivatives 726 N-acyl-α-amino acid derivatives acetylcholinesterase (AChE) inhibitor 1496 – synthesis 1197 acetylide ligand acylamidines 1469 – on photocatalytic H2 production 1668 N-acyl amino acids 1535 N-acetylmannosamine (ManNAc) 920 acylases 913 (+)-achalensolide, asymmetric synthesis 1300 N-acyl cyclic amines 1535 acid–amine coupling 1429 acyl hydrazones, with Rh/duphos 633 – boron derivative 1429 acyl ligand 103 acid–base interactions 860 acyl palladium complex 169 acid halides 525 acylphosphite 838 acidic hydrogen ion 492 1-adamantanol 1533 π-acidic ligands 1404 adapalene 429 acidic phosphate electrolyte, electrochemical adenine-thymine (A-T) 858 properties 1142 adiabatic flash 100 acids, promotor effect 1268 adipic acid Acinetobacter calcoaceticus 908 – fermentation of 1617 – NCIMB 9871 909 – production from LA 1629 acridine-based bisphosphine ligand 1629 aerobic oxidation 1057 acrolein acetal, Heck arylation of 974 Ag/Al2O3 catalyst 1445 acrolein, arylation 974 alcohol dehydrogenase (ADH) 901, 903 Applied Homogeneous Catalysis with Organometallic Compounds: A Comprehensive Handbook in Four Volumes, Third Edition.
    [Show full text]
  • TRANSITION-METAL-CATALYZED HYDROACYLATION Vy M. Dong, Kevin G. M. Kou, and Diane N. Le Department of Chemistry, University of Ca
    TRANSITION-METAL-CATALYZED HYDROACYLATION Vy M. Dong, Kevin G. M. Kou, and Diane N. Le Department of Chemistry, University of California, Irvine, California 92697-2025, United States Vy M. Dong: [email protected] ACKNOWLEDGEMENTS Our work in this area has been supported by UC Irvine, the National Institutes of Health (GM105938), and NSERC. We also acknowledge Paul Feldman for his editorial assistance in compiling the chapter as well as Scott Denmark for the opportunity to contribute to Organic Reactions. INTRODUCTION Transition-metal catalysis has revolutionized the way natural products and medicinal targets are made. For example, asymmetric hydrogenation, olefin metathesis, and cross-coupling have evolved into indispensable tools for drug discovery. As a complement to these well-established strategies, the metal-catalyzed activation of C─H bonds is an increasingly valuable and attractive approach. In metal-catalyzed hydroacylation, an aldehyde C─H bond is oxidized to generate either a C─C bond or C─O bond, depending on the coupling partner used (e.g., alkene, alkyne, or carbonyl compound). This strategy represents an attractive, atom-economical approach for building both ketones and esters from aldehydes (Scheme 1). (1) To date, hydroacylation is most well-established for the preparation of five-membered rings, typically by rhodium catalysis. As the tether between the aldehyde and the unsaturated coupling partner becomes longer, decarbonylation becomes favored over hydroacylation. Similarly, the rate of decarbonylation is usually greater than the rate of hydroacylation in intermolecular reactions. The desired transformation is more favorable, however, when coodinating or directing groups are present on the substrate (Schemes 2 and 3).
    [Show full text]
  • Recent Advances in the Application of Chiral Phosphine Ligands in Pd-Catalysed Asymmetric Allylic Alkylation
    Molecules 2011, 16, 970-1010; doi:10.3390/molecules16010970 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Review Recent Advances in the Application of Chiral Phosphine Ligands in Pd-Catalysed Asymmetric Allylic Alkylation Itzel Guerrero Rios, Alonso Rosas-Hernandez and Erika Martin * Departamento de Química Inorgánica, Facultad de Química, Universidad Nacional Autónoma de México, Av. Universidad 3000, 04510 México D.F., Mexico * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel: +52 55 5622 3720; Fax: +52 55 5622 3720. Received: 20 December 2010; in revised form: 18 January 2011 / Accepted: 19 January 2011 / Published: 21 January 2011 Abstract: One of the most powerful approaches for the formation of simple and complex chiral molecules is the metal-catalysed asymmetric allylic alkylation. This reaction has been broadly studied with a great variety of substrates and nucleophiles under different reaction conditions and it has promoted the synthesis of new chiral ligands to be evaluated as asymmetric inductors. Although the mechanism as well as the active species equilibria are known, the performance of the catalytic system depends on the fine tuning of factors such as type of substrate, nucleophile nature, reaction medium, catalytic precursor and type of ligand used. Particularly interesting are chiral phosphines which have proved to be effective asymmetric inductors in several such reactions. The present review covers the application of phosphine-donor ligands in Pd-catalysed asymmetric allylic alkylation in the last decade. Keywords: allylic alkylation; asymmetric catalysis; chiral phosphines; palladium 1. Introduction During the last decades, transition-metal catalysed reactions have played an important role in asymmetric organic synthesis by providing easy, selective, doable and environmentally friendly processes to produce a wide variety of organic products [1,2].
    [Show full text]
  • Intramolecular Hydroacylation of Allyl Amines Final Paper
    NOTICE The copyright law of the United States (Title 17, United States Code) governs the making of reproductions of copyrighted material. One specified condition is that the reproduction is not to be "used for any purpose other than private study, scholarship, or research." If a user makes a request for, or later uses a reproduction for purposes in excess of "fair use," that user may be liable for copyright infringement. RESTRICTIONS: This student work may be read, quoted from, cited, for purposes of research. It may not be published in full except by permŝssion of the author. WĞƌƌĞƋƵĞƐƚĨƌŽŵ ĂƵƚĂƵƚŚŽƌƉůĞĂƐĞĚŽŶŽƚƌĞƉƌŽĚƵĐĞƚŚŝƐǁŽƌŬŝŶƉƌŝŶƚ͘ŚŽƌƉůĞĂƐĞ ĚŽŶŽƚƌĞƉƌŽĚƵĐĞƚŚŝƐǁŽƌƌŬŝŶŶƉƌŝŶƚ͘ Rhodium-Catalyzed Intramolecular Hydroacylation of Allyl Amines: Optimization and Scope Katherine A. Wellmon Monday, April 22, 2013 Honors Thesis Dr. Bendorf 2 Abstract: There are multiple compounds that are of pharmaceutical interest that contain a benzazepine core. Intramolecular hydroacylation of allylaminobenzaldehyde derivatives provide a route to synthesize benzazepines. The conditions for this hydroacylation have been optimized and a tandem hydroacylation-in situ deprotection of N,N-diallylaminobenzaldehyde has been developed. The allylaminobenzaldehydes were prepared in a 3-step synthesis from N- methylanthranilic acid and N,N-diallylaminobenzaldehyde was prepared in a 2-step synthesis from aminobenzylalcohol. Upon reaction with cationic rhodium catalyst these allylaminobenzaldehydes yielded benzazepines. Introduction and Background: Hydroacylation is defined as the addition of an aldehyde to an alkene. The intramolecular hydroacylation of a molecule containing both of these functional groups can be used to create a cyclized product. Ideally this would provide a wide range of cyclic products. However, intramolecular hydroacylation is limited with respect to the size of the rings that can be produced.
    [Show full text]
  • Universitat Rovira I Virgili Hydroacylation and C-N Coupling Reactions
    UNIVERSITAT ROVIRA I VIRGILI HYDROACYLATION AND C-N COUPLING REACTIONS. MECHANISTIC STUDIES AND APPLICATION IN THE NUCLEOSIDE SYNTHESIS Patricia Marcé Villa ISBN:978-84-691-8840-8/DL: T-1262-2008 UNIVERSITAT ROVIRA I VIRGILI Hydroacylation and C-N Coupling Reactions. Mechanistic Studies and Application in the Nucleoside Synthesis Patricia Marcé Villa Dissertation presented to receive the degree of Doctor of the Universitat Rovira i Virgili, European Mention UNIVERSITAT ROVIRA I VIRGILI Departament de Química Analítica i Química Orgànica Tarragona, Abril 2008 UNIVERSITAT ROVIRA I VIRGILI HYDROACYLATION AND C-N COUPLING REACTIONS. MECHANISTIC STUDIES AND APPLICATION IN THE NUCLEOSIDE SYNTHESIS Patricia Marcé Villa ISBN:978-84-691-8840-8/DL: T-1262-2008 UNIVERSITAT ROVIRA I VIRGILI HYDROACYLATION AND C-N COUPLING REACTIONS. MECHANISTIC STUDIES AND APPLICATION IN THE NUCLEOSIDE SYNTHESIS Patricia Marcé Villa ISBN:978-84-691-8840-8/DL: T-1262-2008 UNIVERSITAT ROVIRA I VIRGILI HYDROACYLATION AND C-N COUPLING REACTIONS. MECHANISTIC STUDIES AND APPLICATION IN THE NUCLEOSIDE SYNTHESIS Patricia Marcé Villa ISBN:978-84-691-8840-8/DL: T-1262-2008 UNIVERSITAT ROVIRA I VIRGILI HYDROACYLATION AND C-N COUPLING REACTIONS. MECHANISTIC STUDIES AND APPLICATION IN THE NUCLEOSIDE SYNTHESIS Patricia Marcé Villa ISBN:978-84-691-8840-8/DL: T-1262-2008 UNIVERSITAT ROVIRA I VIRGILI DEPARTAMENT DE QUIMICA ANALITICA I QUIMICA ORGANICA C/ Marcel.lí Domingo s/n Campus Sescelades 43007 Tarragona Tel. 34 977 55 97 69 Fax 34 977 55 84 46 e-mail: [email protected] Sergio Castillón Miranda, Catedràtic del Departament de Química Analítica i Química Orgànica de la Universitat Rovira i Virgili, CERTIFICA: Que el present treball titulat: “Hydroacylation and C-N Coupling Reactions.
    [Show full text]