Rhodium Catalyzed Hydroformylation

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Format: Hardcover
Pub. Date: 2000-10-01
Publisher(s): Kluwer Academic Pub
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Summary

In the last decade there have been numerous advances in the area of rhodium-catalyzed hydroformylation, such as highly selective catalysts of industrial importance, new insights into mechanisms of the reaction, very selective asymmetric catalysts, in situ characterization and application to organic synthesis. The views on hydroformylation which still prevail in the current textbooks have become obsolete in several respects. Therefore, it was felt timely to collect these advances in a book. The book contains a series of chapters discussing several rhodium systems arranged according to ligand type, including asymmetric ligands, a chapter on applications in organic chemistry, a chapter on modern processes and separations, and a chapter on catalyst preparation and laboratory techniques. This book concentrates on highlights, rather than a concise review mentioning all articles in just one line. The book aims at an audience of advanced students, experts in the field, and scientists from related fields. The didactic approach also makes it useful as a guide for an advanced course.

Table of Contents

Preface xi
Introduction to hydroformylation
1(14)
Piet W. N. M. van Leeuwen
History of phosphorus ligand effects
1(5)
Hydroformylation
6(2)
Ligand parameters
8(7)
Hydroformylation with unmodified rhodium catalysts
15(20)
Raffaello Lazzaroni
Roberta Settambolo
Aldo Caiazzo
Introduction
15(1)
Regioselectivity in the rhodium-catalyzed hydroformylation of vinyl and vinylidenic substrates
16(6)
Catalyst precursors
17(1)
Influence of the alkene structure on the regioselectivity
17(4)
Influence of temperature
21(1)
Influence of CO and H2 partial pressures
22(1)
Mechanism of the hydroformylation of vinyl and vinylidenic alkenes
22(7)
Activation of the catalyst precursor
24(1)
Behavior of the isomeric alkyl-metal intermediates via deuterioformylation
24(4)
In situ IR investigation of the formation and reactivity of acylrhodium intermediates
28(1)
Origin of the regioselectivity
29(6)
Influence of the nature of the substrate
29(2)
Influence of the reaction parameters
31(4)
Rhodium phosphite catalysts
35(28)
Paul C. J. Kamer
Joost N. H. Reek
Piet W. N. M. van Leeuwen
Introduction
35(2)
Monophosphites
37(7)
Catalysis
37(3)
Mechanistic and kinetic studies
40(4)
Diphosphites
44(11)
Catalysis
44(4)
Mechanistic and kinetic studies
48(7)
Hydroformylation of internal alkenes
55(4)
Hydroformylation of less reactive internal and functionalized alkenes
55(2)
Formation of linear aldehydes starting from internal alkenes
57(2)
Calixarene based phosphites
59(4)
Phosphines as ligands
63(44)
Piet W. N. M. van Leeuwen
Charles P. Casey
Gregory T. Whiteker
Monophosphines as ligands
63(13)
Introduction
63(1)
The mechanism
64(2)
Ligand effects
66(2)
In situ studies
68(1)
Kinetics
69(3)
Regioselectivity
72(3)
Conclusion
75(1)
Diphosphines as ligands
76(31)
Introduction
76(2)
Ferrocene based diphosphine ligands
78(4)
BISBI ligands and the natural bite angle
82(5)
Xantphos ligands: tunable bite angles
87(9)
The mechanism, regioselectivity, and the bite angle. Concluding remarks
96(11)
Asymmetric hydroformylation
107(38)
Carmen Claver
Piet W.N.M. van Leeuwen
Introduction
107(2)
Rhodium systems with chiral diphosphite ligands
109(15)
C2 Symmetric chiral diphosphite ligands
109(2)
Catalyst preparation and hydroformylation
111(2)
Characterisation of RhH(L)(CO)2 intermediates. Solution structures of hydroformylation catalysts
113(2)
Structure versus stability and enantioselectivity
115(1)
Chiral cooperativity and effect of substituents in diastereomeric diphosphite ligands
116(5)
C1 Sugar backbone derivatives. Diphosphinite and diphosphite ligands
121(3)
Phosphine-phosphite rhodium catalysts
124(7)
Introduction
124(1)
Rhodium complexes with BINAPHOS and related ligands
124(3)
RhH(CO)2(BINAPHOS) complexes; models for enantioselectivity
127(2)
Separation studies for the BINAPHOS system
129(1)
Chiral phosphine-phosphite ligands containing a stereocenter in the backbone
129(2)
Diphosphine rhodium catalysts
131(7)
Introduction
131(1)
C1 Diphosphines as chiral ligands
131(1)
C2 Diphosphines as chiral ligands
132(4)
The Rh/BDPP system. HPNMR and HPIR studies under hydroformylation conditions
136(2)
Mechanistic considerations
138(7)
Regioselectivity
138(2)
Enantioselectivity and conclusions
140(5)
Hydroformylation in organic synthesis
145(44)
Sergio Castillon
Elena Fernandez
Introduction
145(1)
Hydroformylation of unfunctionalized alkenes
146(3)
Hydroformylation of functionalized alkenes
149(6)
Substrate directed stereoselectivity
155(5)
Control of the regio- and stereoselectivity by heteroatomdirected hydroformylation
160(4)
Consecutive processes under hydroformylation conditions
164(14)
Hydroformylation-acetalization (intramolecular)
165(1)
Hydroformylation-acetalization (intermolecular)
166(2)
Hydroformylation-amination (intramolecular)
168(4)
Hydroformylation-amination-reduction. Hydroaminomethylation
172(3)
Consecutive hydroformylation-aldol reaction
175(2)
Consecutive hydroformylation-Wittig reaction
177(1)
Alkyne hydroformylation
178(4)
Conclusion
182(7)
Aqueous biphasic hydroformylation
189(14)
Jurgen Herwig
Richard Fischer
Principles of biphasic reactions in water
189(2)
Why two-phase catalysis? Scope and Limitations
189(1)
Concepts for two-phase hydroformylation
190(1)
Hydroformylation of propene and butene
191(8)
Historic overview of two-phase hydroformylation technology
191(1)
Ligand developments
191(2)
Kinetics and catalyst pre-formation
193(3)
Process description
196(1)
Status of the operated plants
197(1)
Economics
198(1)
Reaction of various alkenes
199(4)
Ethylene to propanal: why not applied?
199(1)
Long-chain alkenes
200(3)
Process aspects of rhodium-catalyzed hydroformylation
203(30)
Peter Arnoldy
Introduction
203(1)
Economics
204(2)
Catalyst selectivity and activity
206(2)
Catalyst selectivity
206(1)
Catalyst activity
207(1)
Catalyst stability; degradation routes, losses and recovery
208(3)
Rhodium loss routes
208(1)
Ligand loss routes
209(1)
Catalyst recovery processes
210(1)
Process concepts
211(9)
Type I: Stripping reactor process/Rh containment in reactor
212(1)
Type II: Liquid recycle process/use of distillative separation
213(2)
Type III: Two-phase reaction/extraction process
215(1)
Type IV: Extraction after one-phase reaction
216(4)
Survey of commercialized processes and new developments
220(13)
Hydroformylation of butenes
220(3)
Branched higher alkenes to mainly plasticizer alcohols
223(1)
Linear higher alkenes to mainly detergent alcohols
223(2)
1,4-Butanediol
225(1)
Nylon monomers
226(7)
Catalyst preparation and decomposition
233(20)
Piet W. N. M. van Leeuwen
Introduction
233(1)
Catalyst preparation
233(2)
Catalyst decomposition
235(14)
Metal plating or cluster formation
235(1)
Oxidation of phosphorus ligands
235(2)
Phosphorus-carbon bond breaking in phosphines
237(6)
Decomposition of phosphites
243(4)
Formation of dormant sites
247(2)
Concluding remarks
249(4)
Novel developments in hydroformylation
253(28)
Joost N. H. Reek
Paul C. J. Kamer
Piet W. N. M. van Leeuwen
Introduction
253(1)
New bimetallic catalysts
253(3)
Novel developments in catalyst separation
256(18)
Micellar catalysis
256(4)
Supported aqueous phase catalysis (SAPC)
260(2)
Hydroformylation in supercritical fluids
262(3)
Fluorous Biphase catalysis
265(2)
Dendrimer supported catalysts
267(2)
Novel developments in polymer supported catalyst
269(5)
Supramolecular catalysis
274(3)
Conclusions
277(4)
Subject index 281

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