Carbonylation of π-allyl systems

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Table of contents

Contents
Abbreviations
General Introduction
Bibliography
CHAPTER I : Transition metal catalyzed domino reactions
Pure domino reactions (TM-DOM)
Pseudo-domino reactions (TM-PDOM)
i. Pseudo-domino type I reactions
ii. Pseudo-domino type II reactions
CHAPTER II : Carbonylation reactions
Foreword
Carbonylation of sp-hybridized carbon atoms
Carbonylation of sp2-hybridized carbon atoms
i. Starting from an alkyne substrate
ii. By oxidative addition of a carbon-halogen bond
1) Cross-coupling reaction
2) Alkoxycarbonylation
3) Aminocarbonylation
4) Carboxylic acids formation
iii. By C-H activation
Carbonylation of sp3 hybridized carbon atoms
i. Carbonylation of π-allyl systems
1) Via carbopalladation
2) Via hydropalladation
iii. Case of benzyl halides
iv. With α-carbon-bound resonance stabilized electron withdrawing groups
1) Carbonylation of α-haloacetates
2) Carbonylation of α-haloketones
Carbonylation within domino reactions
CHAPTER III : Decarboxylative Allylation
Introduction
Catalysis by the transition metals
Mechanism
Decarboxylative allylation with other electron withdrawing groups
Results and Discussion
CHAPTER IV : Execution of the project
Development of new Pd-catalyzed domino sequences involving carbon a)monoxide
The requirement of a sequential study
i. Trials at atmospheric pressure
ii. Carbonylation of α-chloroketones
iii. Decarboxylative allylation
Optimization
i. Preliminary results
ii. Pressure
iii. Catalyst loading
iv. Used of a co-solvent and influence of the base
v. Screening of ligands
Scope and limitation of the pseudo-domino sequence
i. Functionalization of α-chloroketones
1) Substitution on the aromatic ring
2) Substitution of the chloroketone at the α-position
ii. Substituted allylic alcohols
Mechanistic studies of the pseudo-domino sequence
i. Oxidative addition at room temperature
ii. Kinetic studies
iii. Study of the C-Pd / O-Pd equilibrium
Conclusion and perspectives
CHAPTER V : Toward a new domino sequence
Introduction
Sequential study with incrementation of the domino sequence
i. Synthesis of the cyclization precursor
ii. Study of the cyclization, trapping with a hydride
iii. Toward a new pseudo-domino type I sequence: « N-allylation / carbopalladation / hydride trapping»
iv. Toward a new triple pseudo-domino type I sequence: «N-allylation / carbopalladation / methoxycarbonylation»
1) With formation of a neopentyl palladium intermediate
2) Study of the competition between the β-hydride elimination and carbonylation
v. Approaches toward the full pseudo-domino sequence
1) Toward the full sequence « N-allylation / carbopalladation / carbonylative / decarboxylative allylation »
2) Switch from allyloxy- to methoxycarbonylation
3) Possible pathways from 34 to 23
vi. Extension to different groups than malonate
1) Planning intermediate β-ketoesters
2) Planning intermediate malononitriles
vii. Approach to a triple pseudo-domino type I sequence: « N-propargylation / 5-exo-dig carbopalladation / carbonylation »
1) Methoxycarbonylation
2) Allyloxycarbonylation
Conclusion and perspectives
General conclusion
Experimental Section
General instrumentation
General procedures (GP)