Description of a pentacoordinated phosphorus

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Table of contents

CHAPTER 1:
PRESENTATION OF ALKYL HYDROGENO-PHENYLPHOSPHINATES
1.1 FROM ASYMMETRIC CATALYSIS TO HYDROGENO-PHOSPHINE OXIDES
1.1.1 Organophosphorous compounds in asymmetric catalysis
1.1.2 Description of secondary phosphine oxides
1.2 SYNTHESIS OF SECONDARY PHOSPHINE OXIDES
1.3 NUCLEOPHILIC SUBSTITUTIONS AT PHOSPHORUS ATOM
1.4 PSEUDOROTATIONS OF PENTACOORDINATED PHOSPHOROUS COMPOUNDS
1.4.1 Description of a pentacoordinated phosphorus
1.4.2 The Berry pseudorotations
1.5 AIM OF THE THESIS
CHAPTER 2:
METHODOLOGIES FOR SYNTHESIS, ANALYSIS, THEORETICAL MODELING AND KINETIC STUDIES
2.1 INTRODUCTION
2.2 THEORETICAL CHEMISTRY
2.2.1 The Schrödinger Equation
2.2.2 Density Functional Theory
2.2.3 Implicit solvation
2.2.4 Effect of the temperature
2.3 SYNTHESIS OF ALKYL HYDROGENO-PHENYLPHOPHINATES
2.4 ANALYSIS METHODS AND QUANTIFICATION
2.4.1 Nuclear magnetic resonance
2.4.2 Chiral high performance liquid chromatography
2.5 KINETICS
2.5.1 Reaction rate and transition standard Gibbs free energy
2.5.2 A case of study: the racemization of ethyl phenylphosphinate
2.6 CONCLUSION
CHAPTER 3:
SYSTEM OF INTEREST AND EQUILIBRIUM IN SOLUTION
3.1 INTRODUCTION
3.1.1 Context
3.1.2 Choice of the system
3.2 CONFORMATION OF THE METHYL HYDROGENO-PHENYLPHOSPHINATE
3.3 PROTOTROPIC EQUILIBRIUM
3.4 ACIDOBASICITY SCALE
3.4.1 How to build an acidobasicity scale
3.4.2 Determination of the pKa of the compounds of interest
3.5 METHOXIDE AND PHOSPHONIDE
3.5.1 Deprotonation of phosphinate by an alkoxide
3.5.2 Inversion of configuration of a phosphinide
3.6 CONCLUSION
CHAPTER 4:
TRANSESTERIFICATION MECHANISM OF METHANOL ON ALKYL HYDROGENOPHENYLPHOSPHINATE
4.1 INTRODUCTION
4.1.1 Context
4.1.2 Methodology
4.2 ADDITION OF METHANOL ONTO THE PHOSPHORUS ATOM
4.2.1 Possible approaches of methanol onto phosphinate
4.2.2 A study of the 6 mechanisms for SN2
4.3 INFLUENCE OF THE PENTACOORDINATED INTERMEDIATE ON THE GLOBAL MECHANISM
4.3.1 Further evolution on the pentacoordinated intermediate
4.3.2 Berry pseudorotations of the pentacoordinated intermediate
4.4 KINETIC STUDY
4.4.1 Experimental measurements
4.4.2 Observations
4.4.3 Discussion
4.4.4 Kinetic adjustment
4.5 RELIABILITY OF SIMULATIONS
4.6 CONCLUSION
CHAPTER 5:
EFFECT OF BASIC CATALYSIS ON THE TRANSESTERIFICATION MECHANISM OF ALKYL HYDROGENOPHENYLPHOSPHINATES BY ALCOHOL
5.1 INTRODUCTION
5.1.1 Context
5.1.2 Methodology
5.2 EXPERIMENTAL STUDY: KINETIC OF ENANTIOMERIZATION
5.2.1 Observations
5.2.2 Kinetic modeling
5.3 EQUILIBRIUM OF THE SYSTEM IN BASIC CONDITIONS
5.3.1 Tautomerism and coordination of TMA
5.3.2 Deprotonation of reactants
5.3.3 Conclusion
5.4 ADDITION MECHANISM IN BASIC CONDITIONS
5.4.1 Addition on phosphinous acid form
5.4.2 With one equivalent of TMA
5.4.3 With 2 equivalents of TMA
5.4.4 Deprotonated phosphinate
5.4.5 The mysterious catalyst
5.4.6 Conclusion
5.5 CONCLUSION
CHAPTER 6:
EFFECT OF THE HINDRANCE ON THE ENANTIOSTABILITY OF ALKYL HYDROGENOPHENYLPHOSPHINATES
6.1 INTRODUCTION
6.1.1 Context
6.1.2 Methodology
6.2 INFLUENCE OF THE ALKYL GROUP ON SN2@P IN NEUTRAL CONDITIONS
6.3 KINETIC STUDY IN BASIC CONDITIONS USING 31P-CPD NMR
6.3.1 Choice of the system
6.3.2 Observations
6.4 EARLY CONCLUSION
GENERAL CONCLUSION