RHODIUM CATALYZED HYDROFORMYLATION

Transcription

1 RHODIUM CATALYZED HYDROFORMYLATION

2 Catalysis by Metal Complexes Volume 22 Editors: B. R. James, The University of British Columbia, Vancouver, Canada P. W. N. M. van Leeuwen, University of Amsterdam, The Netherlands Advisory Board: I. Horváth, Exxon Corporate Research Laboratory, Annandale, NJ, U.S.A. S. D. Ittel, E. I. du Pont de Nemours Co., Inc., Wilmington, Del., U.S.A. A. Nakamura, Osaka University, Osaka, Japan W. H. Orme-Johnson, M.I.T, Cambridge, Mass., U.S.A. R. L. Richards, John Innes Centre, Norwich, U.K. A. Yamamoto, Waseda University, Tokyo, Japan The titles published in this series are listed at the end of this volume.

3 RHODIUM CATALYZED HYDROFORMYLATION Edited by PIET W.N.M. VAN LEEUWEN Institute of Molecular Chemistry, University of Amsterdam, Amsterdam, The Netherlands and CARMEN CLAVER Department de Quimica Física i Inorgánica, Universitat Rovira i Virgili, Tar ragona, Spain KLUWER ACADEMIC PUBLISHERS NEW YORK / BOSTON / DORDRECHT/ LONDON / MOSCOW

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5 TABLE OF CONTENTS Preface xi 1 Introduction to hydroformylation 1 Piet W. N. M. van Leeuwen 1.1 History of phosphorus ligand effects Hydroformylation Ligand parameters 8 2 Hydroformylation with unmodified rhodium catalysts 15 Raffaello Lazzaroni, Roberta Settambolo and Aldo Caiazzo 2.1 Introduction Regioselectivity in the rhodium-catalyzed hydroformylation of vinyl and vinylidenic substrates Catalyst precursors Influence of the alkene structure on the regioselectivity Influence of temperature Influence of CO and H2 partial pressures Mechanism of the hydroformylation of vinyl and vinylidenic alkenes Activation of the catalyst precursor Behavior of the isomeric alkyl-metal intermediates via deuterioformylation In situ IR investigation of the formation and reactivity of acylrhodium intermediates Origin of the regioselectivity Influence of the nature of the substrate Influence of the reaction parameters 31 3 Rhodium phosphite catalysts 35 Paul C. J. Kamer, Joost N. H. Reek, and Piet W. N. M. van Leeuwen 3.1 Introduction 35 v

6 vi Table of contents 3.2 Monophosphites Catalysis Mechanistic and kinetic studies Diphosphites Catalysis Mechanistic and kinetic studies Hydroformylation of internal alkenes Hydroformylation of less reactive internal and functionalized alkenes Formation of linear aldehydes starting from internal alkenes Calixarene based phosphites 59 4 Phosphines as ligands 63 Piet W. N. M. van Leeuwen, Charles P. Casey, and Gregory T. Whiteker 4.1 Monophosphines as ligands Introduction The mechanism Ligand effects In situ studies Kinetics Regioselectivity Conclusion Diphosphines as ligands Introduction Ferrocene based diphosphine ligands BISBI ligands and the natural bite angle Xantphos ligands: tunable bite angles The mechanism, regioselectivity, and the bite angle. Concluding remarks 96 5 Asymmetric hydroformylation 107 Carmen Claver and Piet W.N.M. van Leeuwen 5.1 Introduction Rhodium systems with chiral diphosphite ligands C 2 Symmetric chiral diphosphite ligands Catalyst preparation and hydroformylation Characterisation of [RhH(L)(CO) ] intermediates. 2 Solution structures of hydroformylation catalysts Structure versus stability and enantioselectivity 115

7 Table of contents vii Chiral cooperativity and effect of substituents in diastereomeric diphosphite ligands C 1 Sugar backbone derivatives. Diphosphinite and diphosphite ligands Phosphine-phosphite rhodium catalysts Introduction Rhodium complexes with BINAPHOS and related ligands [RhH(CO) 2(BINAPHOS)] complexes; models for enantioselectivity Separation studies for the BINAPHOS system Chiral phosphine-phosphite ligands containing a stereocenter in the backbone Diphosphine rhodium catalysts Introduction C 1 Diphosphines as chiral ligands C2 Diphosphines as chiral ligands The Rh/BDPP system. HPNMR and HPIR studies under hydroformylation conditions Mechanistic considerations Regioselectivity Enantioselectivity and conclusions Hydroformylation in organic synthesis 145 Sergio Castillón and Elena Fernández 6.1 Introduction Hydro formylation of unfunctionalized alkenes Hydroformylation of functionalized alkenes Substrate directed stereoselectivity Control of the regio- and stereoselectivity by heteroatomdirected hydro formy lation Consecutive processes under hydroformylation conditions Hydroformylation-acetalization (intramolecular) Hydroformylation-acetalization (intermolecular) Hydroformylation-amination (intramolecular) Hydroformylation-amination-reduction. Hydroaminomethylation Consecutive hydroformylation-aldol reaction Consecutive hydroformylation-wittig reaction Alkyne hydroformylation Concluding remarks 182

8 viii Table of contents 7 Aqueous biphasic hydroformylation 189 Jürgen Herwig and Richard Fischer 7.1 Principles of biphasic reactions inwater Why two-phase catalysis? Scope and Limitations Concepts for two-phase hydroformylation Hydroformylation of propene and butene Historic overview of two-phase hydroformylation technology Ligand developments Kinetics and catalyst pre-formation Process description Status of the operated plants Economics Reaction of various alkenes Ethylene to propanal: why not applied? Long-chain alkenes Process aspects of rhodium-catalyzed hydroformylation 203 Peter Arnoldy 8.1 Introduction Economics Catalyst selectivity and activity Catalyst selectivity Catalyst activity Catalyst stability; degradation routes, losses and recovery Rhodium loss routes Ligand loss routes Catalyst recovery processes Process concepts Type I: Stripping reactor process/rh containment in reactor Type II: Liquid recycle process/use of distillative separation Type III: Two-phase reaction/extraction process Type IV: Extraction after one-phase reaction Survey of commercialized processes and new developments Hydroformylation of butenes Branched higher alkenes to mainly plasticizer alcohols 223

9 Table of contents ix Linear higher alkenes to mainly detergent alcohols ,4-Butanediol Nylon monomers Catalyst preparation and decomposition 233 Piet W. N. M. van Leeuwen 9.1 Introduction Catalyst preparation Catalyst decomposition Metal plating or cluster formation Oxidation of phosphorus ligands Phosphorus-carbon bond breaking in phosphines Decomposition of phosphites Formation of dormant sites Concluding remarks Novel developments in hydroformylation 253 Joost N. H. Reek, Paul C. J. Kamer, and Piet W. N. M. van Leeuwen 10.1 Introduction New bimetallic catalysts Novel developments in catalyst separation Micellar catalysis Supported aqueous phase catalysis (SAPC) Hydroformylation in supercritical fluids Fluorous Biphase catalysis Dendrimer supported catalysts Novel developments in polymer supported catalyst Supramolecular catalysis Conclusions 277 Index 28 1

10 Preface This book covers the developments in rhodium catalyzed hydroformylation of the last decade, one of the most important reactions in industry catalyzed by homogeneous catalysts. The work includes many of the advances that have been made by academic and industrial researchers. The field has undergone drastic changes, both in its industrial applications and in our understanding. Clearly, the new advances pose new problems and set new targets for future research. In spite of the importance of the field, the last reviews covering a broad area in hydroformylation are outdated (Falbe 1980, Pruett 1977) and it was felt timely to bring together the recent developments. Only in the area of aqueous biphasic hydroformylation there are several exhausting reviews available. This is the first monograph on hydroformylation of this type and for other processes there not many examples. The aim of the book is to review the mainstream of the activities in the field and not to present a complete coverage of the literature, not even the recent literature. Several thousands of papers and patents deal with rhodiumcatalyzed hydroformylation and a complete review would be impossible. We have chosen for a more didactic approach, in which we have tried to avoid one-liners about publications. In the book one will find typical examples about kinetics, applications in organic chemistry, industrial processes, mechanistic understanding, etc. In the mainstream activities we have tried to include industrial developments. We may have missed new catalyst systems that are as yet small but may turn out to be of major importance later, but that can hardly be avoided. New and important developments involving other metals, such as cobalt, platinum, and palladium will also be absent. While writing we had a broad audience in mind: chemists and engineers in industry and academia with an interest in homogeneous catalysis, whose backgrounds may be as varied as those of the present authors: inorganic, organic, organometallic, catalytic, chemical engineering. It is hoped that specialists in one area will read with interest the chapters on the neighbouring expertise. The book is also meant for PhD-students and advanced students interested in this area. The combination of topics we have chosen is rather unique, connecting studies on ligand effects, catalyst characterization, industrial requirements regarding stability and separation, catalyst decomposition, and applications xi

11 xii Preface in fine and bulk chemistry. The reader will notice the importance of one discipline for the other. In many cases these relationships have already been established, but for other cases the book might assist future developments. The key roles that ligands may play in selectivity may be an eye-opener for organic chemists and it will further enhance the large number of new applications and reactions that are being discovered. The comments in several chapters on catalyst preparation and feed purification may be useful for scientists who are not specialized in homogeneous catalysis using transition metal complexes. Hydroformylation is also a model reaction system in homogeneous catalysis as it contains so many aspects such as ligand effects (electronic, steric, bite angle), in situ studies, complicated kinetics, and effects of conditions and impurities. All this, combined with its practical value, makes it an ideal topic in education. The editors are very grateful to the authors for the good work they did and the prompt responses. The writing took only a few months, as did the production by the publisher. Writing the book has been rewarding, because we learnt many things. Most of all perhaps, we obtained a clearer view on what we still don t fully understand. Amsterdam, Tarragona Piet van Leeuwen, Carmen Claver