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Niveau: Secondaire, Lycée, Terminale
PALLADACYCLES: SYNTHESIS AND CATALYSIS ACADEMISCH PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Universiteit van Amsterdam op gezag van de Rector Magnificus Prof. dr. D.C. van den Boom ten overstaan van een door het college voor promoties ingestelde commissie, in het openbaar te verdedigen in de Agnietenkapel op vriidag 29 februari 2008, te 14:00 uur door Alexandre Holuigue geboren te Colmar, Frankrijk

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cyclopalladated compounds

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Publié par	profil-shuwyag-2012
Nombre de lectures	48
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PALLADACYCLES:
SYNTHESIS AND CATALYSIS

ACADEMISCH PROEFSCHRIFT

ter verkrijging van de graad van doctor
aan de Universiteit van Amsterdam
op gezag van de Rector Magnificus
Prof. dr. D.C. van den Boom
ten overstaan van een door het college voor promoties
ingestelde commissie,
in het openbaar te verdedigen in de Agnietenkapel
op vriidag 29 februari 2008, te 14:00 uur

door

Alexandre Holuigue

geboren te Colmar, Frankrijk Promotiecommissie

Promotor: Prof. dr. C.J. Elsevier

Co-promotor: Prof. dr. M. Pfeffer

Overige Leden: Prof. dr. H. Hiemstra
Prof. dr. P. Pale
Prof. dr. J.N.H. Reek
Dr. F. Hartl G. Rothenberg

Faculteit der Natuurwetenschappen, Wiskunde en Informatica

ISBN number: 90-9022752-8

Het in dit proefschrift beschreven onderzoek is uitgevoerd in het Van ’t Hoff Institute for
Molecular Sciences (HIMS), Faculteit der Natuurwetenschappen, Wiskunde en
Informatica van de Universiteit van Amsterdam. Discipline: Chimie

PALLADACYCLES :
SYNTHESIS AND CATALYSIS

Thèse de Doctorat pour obtenir le grade de
Docteur de l’Université Louis Pasteur Strasbourg I
présentée par

Alexandre Holuigue

Soutenue publiquement le 29 Février 2008

Dirigée par C.J. Elsevier et M. Pfeffer
et co-encadrée par C. Sirlin

Membres du Jury :

C.J. Elsevier Professeur à l’Université d’Amsterdam (UVA), Pays-Bas
H. Hiemstra iversité d’Amsterdam (UVA), Pays-Bas
P. Pale iversité Louis Pasteur (ULP), Strasbourg
J.N.H. Reek Professeur à l’Univ
F. Hartl Maître de Conférences à l’Université d’Amsterdam, Pays-Bas
G. Rothenberg Professeur Associé à l’Université d’Amsterdam, Pays-Bas
M. Pfeffer Directeur de Recherches au C.N.R.S., Strasbourg
C. Sirlin Maître de Conférences à l’Université Louis Pasteur, Strasbourg Table of Contents

1 General Introduction 1
1.1 Coordination and Organometallic Complexes 1
1.2 Metallacyclic and Cyclometallated Compounds of the
Transition Elements 2
1.2.1 Metallacyclic compounds 2
1.2.2 Cyclometallated compounds 3
1.3 Formation of Palladacyclic Compounds 4
1.3.1 Insertion into C–C bonds 4
1.3.2 Reaction with dilithio and di-Grignard reagents 5
1.3.3 Palladacycles derived from homocoupling reactions
of alkynes or alkenes 5
1.3.4 Palladacycles derived from heterocoupling reactions
of unsaturated molecules, polyalkene or polyalkyne 6
1.3.5 Formation of palladacycles via palladacyclization reactions 7
1.4 Formation of Cyclopalladated Compounds 9
1.4.1 Cyclopalladation by orthopalladation and similar reactions 9
1.4.2 Cyclopalladation via oxidative addition 10
1.4.3 Cyclopalladated compounds formed by transmetalation reaction 11
1.4.4 Cyclopalladated compounds formed by transcyclometalation
reaction 13
1.4.5 Cyclopalladation via carbopalladation of alkenes and
chloropalladation of alkynes 13
1.4.5.1 Alkoxy- and carbopalladation of allylic amines and thioethers 13
1.4.5.2 Trans-chloropalladation of heterosubstituted alkynes 14
1.5 Palladacyclic and Cyclopalladated Compounds in Catalysis 15
1.5.1 Palladacyclic compounds 15
1.5.1.1 Palladacycles as intermediates: 6-membered rings
and larger rings 15
1.5.1.2 Palladacycles as intermediates: 5-membered rings
and smaller rings 17
1.5.1.3 Palladacycles as catalysts 17 1.5.2 Cyclopalladated compounds 18
1.6 Aim and Outline of this Thesis 20
1.7 References 21

2 Synthesis and Characterization of Palladacyclopentadienes
Obtained from Dissymmetric Alkynes 27
2.1 Introduction 28
2.2 Results 29
2.2.1 Synthesis of palladacyclopentadienes from
methyl phenylpropynoate 30
2.2.2 Synthesis of palladac
methyl (4-methoxyphenyl)propynoate 31
2.2.3 Synthesis of palladacyclopentadienes from
methyl (4-nitrophenyl)propynoate 31
2.2.4 X-ray crystal structures of several palladacyclopentadiene
compounds 33
2.3 Discussion 37
2.3.1 Regioselectivity of the second alkyne insertion 37
2.3.2 Reactivity of palladacyclopentadienes towards alkynes 39
2.3.2.1 Stability of the regioisomers 39
2.3.2.2 Exchange reaction 41
2.3.2.3 Cyclotrimerization reaction of
methyl (4-nitrophenyl)propynoate 42
2.4 Conclusion 45
2.5 Experimental Section 46
2.5.1 General considerations 46
2.5.2 Synthesis 46
2.5.3 Probing of interconversion and alkyne exchange
concerning the mixtures of regioisomers 54
2.5.4 X-ray crystal structure analyses 56
2.5.5 Acknowledgement 57
2.6 References 57

3 Mechanistic and Kinetic Investigation of the Conversion
of Dimethyl-2-butynedioate to Conjugated (Z,Z)-Dienes
Catalyzed by [Pd(4-CH -C H -bian)(CCOOMe)] 61 3 6 4 4
3.1 Introduction 62
3.2 Results and Discussion 64
3.2.1 Catalytic three-component synthesis of
conjugated dienes from alkynes 64
3.2.2 Kinetic aspects of the catalytic three-component
synthesis of conjugated dienes from alkynes 69
2 23.2.2.1 [Pd(NN)( η -DMF)] and [Pd(NN)( η -alkyne)] complexes
involved in the catalysis 69
23.2.2.2 Reactivity of organic halide with [Pd(bipy)( η -DMF)],
2 [Pd(bipy)( η -dmbd)] and palladacyclopentadiene complexes 72
3.2.2.3 Reaction involving the σ-dienylpalladium complex 72
3.2.3 Mechanism of the reaction of dmbd, organic halide
and organotin reagent catalyzed by [Pd(NN)(CCOOMe)] 74 4
3.3 Conclusion 76
3.4 Experimental Section 77
3.4.1 General considerations 77
3.4.2 Catalytic synthesis of conjugated diene 77
3.4.3 Kinetic and mechanistic study 79
3.4.4 Acknowledgement 81
3.5 References 81

4 Synthesis of Cyclopalladated and Cycloplatinated Complexes
and their Application as Sonogashira Coupling Catalysts 83
4.1 Introduction 84
4.2 Results and Discussion 86
4.2.1 Synthesis of the cyclometalated complexes 86
4.2.2 X-ray structure determinations of [Pt(bzq)(dppe)]PF and 6
[Pd(bzq)(dppe)]PF 88 6
4.2.3 Sonogashira reaction catalyzed by
cyclopalladated complexes 90
4.2.4 Research of a cyclopalladated complex more catalyst
than pre-catalyst 91
4.2.4.1 How do the palladacycles act in catalytic reactions? 91
∧4.2.4.2 Stabilization of zerovalent CN-palladacycles 92
4.3 Conclusion 95
4.4 Experimental Section 95
4.4.1 General considerations 95
4.4.2 Synthesis 96
4.4.3 Cross-coupling of 4-bromobenzonitrile with phenylacetylene 101
4.4.4 X-ray crystal structure analyses 101
4.5 References 104

0 25 [Pd (Ar-bian)( η -Alkene)] Complexes Catalyze Chemo- and
Stereoselective Partial Hydrogenation of Functional 1,2-Dienes 107
5.1 Introduction 108
5.2 Results and Discussion 110
0 25.2.1 [Pd (Ar-bian)( η-alkene)] complexes 110
5.2.2 Hydrogenation of the 1,2-dienyl phosphonates 110
5.2.3 Hydrogenation of the 2,3-dienoates 112
5.2.4 Stereoselectivity and Z-E isomerization 114
5.2.5 Mechanistic aspects 115
5.3 Conclusion 117
5.4 Experimental Section 117
5.4.1 General considerations 117
5.4.2 Hydrogenation experiments 118
5.4.3 Acknowledgement 118
5.5 References 119

Samenvatting 121

Summary 125

Résumé 129
List of Abbreviations 133

List of Publications 135

Acknowledgements 137

Chapter 1

General Introduction

1.1 Coordination and Organometallic complexes

Organometallic and coordination chemistry are two domains of chemistry that are
complementary. Coordination complexes consist of one or more metals centres
surrounded by ligands, organic or inorganic, ions or molecules, that can have an
independent existence. The organometallic chemistry is defined as the chemistry of
compounds containing metal–carbon bond, however, in general manner this term is
1attributed to the chemistry made of organic transformations assisted by metals.
The rise of the modern organometallic chemistry occured in the 50’s, after the
2a 2bdiscovery of the ferrocene (1951) by Pauson and Miller and the elucidation of its
2c 2dstructure (1952) by Wilkinson and Fischer . However, it is in 1757 that the origin of
the organometallic chemistry can be traced back when Cadet de Gassicourt
discovered the “Cadet&#

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