AQUEOUS ORGANOMETALLIC CATALYSIS

Transcription

1 AQUEOUS ORGANOMETALLIC CATALYSIS

2 Catalysis by Metal Complexes Volume 23 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 AQUEOUS ORGANOMETALLIC CATALYSIS by FERENC JOÓ Institute of Physical Chemistry, University of Debrecen and Research Group of Homogeneous Catalysis, Hungarian Academy of Sciences, Debrecen, Hungary KLUWER ACADEMIC PUBLISHERS NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW

4 ebook ISBN: Print ISBN: Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow Print 2001 Kluwer Academic Publishers Dordrecht All rights reserved No part of this ebook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: and Kluwer's ebookstore at:

5 Table of Contents Preface ix Introduction 1.1 A personal look at the history of aqueous organometallic catalysis 1.2 General characteristics of aqueous organometallic catalysis Ligands used for aqueous organometallic catalysis 2.1 Tertiary phosphine ligands with sulfonate or alkylene sulfate substituents Direct sulfonation Nucleophilic phosphinations, Grignard-reactions and catalytic cross-coupling for preparation of sulfonated phosphines Addition reactions Tertiary phosphine ligands with nitrogen-containing substituents Phosphine ligands with carboxyl substituents Hydroxyl-substituted water-soluble tertiary phosphines Macroligands in aqueous organometallic catalysis Bis[2-(diphenylphosphino)ethyl]amine - a versatile starting material for chelating bisphosphines Tertiary phosphines with phosphonate and phosphonium substituents Water-soluble ligands for aqueous organometallic catalysis - latest developments Solubilities of tertiary phosphines and their complexes in water Hydrogenation 3.1 Hydrogenation of olefins Catalysts with simple ions as ligands Ruthenium salts as hydrogenation catalysts v

6 vi Hydridopentacyanocobaltate(III) Water-soluble hydrogenation catalysts other than simple complex ions Catalysts containing phosphine ligands Hydrogenation of olefins with miscellaneous water-soluble catalysts without phosphine ligands Mechanistic features of hydrogenation of olefins in aqueous systems Water-soluble hydrogenation catalysts with macromolecular ligands Enantioselective hydrogenations of prochiral olefins Effect of amphiphiles on the enantioselective hydrogenation of prochiral olefins in water Hydrogenation of arenes and heteroarenes in aqueous systems Hydrogenation of aldehydes and ketones Hydrogenation of miscellaneous organic substrates Hydrogenation of nitro compounds and imines Transfer hydrogenation and hydrogenolysis Hydrogenation of carbon dioxide in aqueous solution Hydrogenations of biological interest Hydrogenation of biological membranes Regeneration of dihydronicotinamide cofactors The water gas shift reaction and hydrogenations with mixtures The water gas shift reaction Hydrogenations with Hydroformylation 4.1 Introduction Rhodium-catalyzed biphasic hydroformylation of olefins. The Ruhrchemie-Rhône Poulenc process for manufacturing butyraldehyde Aqueous/organic biphasic hydroformylation butenes and other alkenes Basic research in aqueous organometallic hydroformylation; ligands and catalysts Mechanistic considerations Effects of water

7 Effects of ph Asymmetric hydroformylation in aqueous media Surfactants in aqueous hydroformylation Water soluble polymeric ligands in aqueous hydroformylation Aqueous extractions for efficient catalyst recovery Synthetic applications Miscellaneous aspects of aqueous-organic biphasic hydroformylation Interphase engineering using promoter ligands Gas-liquid-liquid reaction engineering vii Carbonylation 5.1 Introduction 5.2 Carbonylation of organic halides 5.3 Carbonylation of methane, alkenes and alkynes 5.4 Carbonylation of alcohols Carbon-carbon bond formation 6.1 Heck reactions in water 6.2 Suzuki couplings in aqueous media 6.3 Sonogashira couplings in aqueous media 6.4 Allylic alkylations in aqueous media 6.5 Catalytic removal of allylic protecting groups 6.6 Stille couplings in aqueous media 6.7 Other catalytic C-C bond formations Miscellaneous reactions Nucleophilic additions to 1,3-dienes; the synthesis of geranylacetone Dimerization, oligomerization and polymerization of alkenes and alkynes Dimerization and polymerization of ethylene Telomerization of dienes Ring-opening metathesis polymerizations in aqueous media Alkyne reactions Alternating copolymerization of alkenes and carbon monoxide

8 viii Catalytic oxidations in aqueous media - recent developments 8.1 Wacker-type oxidations 8.2 Oxidations with and Miscellaneous catalytic reactions in aqueous media 9.1 Aqueous organometallic catalysis under traditional conditions 9.2 Emerging techniques Host-guest chemistry in aqueous organometallic catalysis 10.1 Cyclodextrins and the formation of inclusion compounds 10.2 Application of cyclodextrins and other host molecules in aqueous organometallic catalysis Index Key to the abbreviations

9 Preface Aqueous organometallic catalysis is a rapidly developing field and there are several reasons for the widespread interest. Perhaps the most important is the possibility of using liquid-liquid two-phase systems for running catalytic reactions. Often termed liquid biphasic catalysis, these two-phase procedures allow recycling of the catalyst dissolved exclusively in one of the phases of course, this book focuses on the aqueous phase. It is this catalyst recycling, together with the much simplified technology, where the interest of the chemical industry lies. Small scale laboratory procedures may also benefit from using organometallic catalysts in aqueous solutions due to the easier, cleaner isolation of the desired products of biphasic reactions. In addition, growing environmental concern forces industry and research laboratories to use less and less environmentally hazardous chemicals, and water as opposed to most organics is certainly an environmentally benign (green) solvent. A somewhat less obvious and less exploited possibility is in that several catalytic reactions which do take place in homogeneous aqueous solutions or in biphasic systems simply do not happen in dry organic solvents. This book is devoted to a systematic description of the basic phenomena, principles and practice of aqueous organometallic catalysis in a relatively concise and organised way. Organisation of the material is not an easy task, since fundamental chemical questions, such as reactivity and selectivity of a catalyst in a given reaction should be treated together with the various synthetic applications and industrial or engineering aspects. Only those systems are described where the catalyst itself is a genuine organometallic compound or where such intermediates are formed along the reaction pathway. Accordingly, those organic syntheses in aqueous solutions where ix

10 x Preface an organometallic compound acts as a stoichiometric reagent are largely omitted. The field of liquid multiphase catalysis expands readily, nevertheless other multiphase techniques are just scarcely mentioned. Among them phase transfer assisted organometallic catalysis is a special approach because there are many cases when the catalyst resides and acts in the aqueous phase or at the aqueous/organic interface. Reactions, where the organometallic catalysis takes place entirely in the organic phase, and phase transfer catalysis is used merely to supply reagents from the aqueous phase are not discussed. Numerous reviews, special journal editions and books have been already devoted to the topic of aqueous organometallic catalysis especially in the last 5-8 years. All these publications, however, comprise of detailed reviews or accounts on particular topics written by leading specialists. While this is certainly beneficial for those who themselves work in the same direction, non-specialists, students or those who are just to enter this field of research may be better served by a monograph of the style and size of the Catalysis by Metal Complexes series. In 1994, in Volume 15 of this series, a chapter was published on aqueous organometallic hydrogenations with the aim of giving a complete description of what had been done before in that respect. After only seven years such an aim of all-inclusivity is irrealistic, and this had to bring with itself a selection of the literature used. Writing of this book took much more time than originally expected. I owe a lot of thanks to D. J. Larner, E. M. C. Lutanie and J. W. Wijnen, Publishing Editors at Kluwer Academic Publishers who helped this long process by their advice and patience. Thanks are due to the American Chemical Society, the Royal Society, Elsevier Science B. V. and Wiley- VCH Verlag GmbH for permissions to use previously published material. All my family, colleagues and students had to survive the consequences of my preoccupation with this task many thanks for their understanding. I am particularly indebted to Gábor Papp for preparing the artwork. Finally, and with utmost appreciation I thank the support and encouragement provided by my wife Dr. Ágnes Kathó. Without her understanding at home, and her invaluable help in literature search, proofreading and in discussions of the various versions of the manuscript this book could have never been completed. Debrecen, September 2001 Ferenc Joó