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Table of contents
Abbreviations
General introduction
Chapter I – Experimental and Theoretical Methods for Mechanistic Studies
1. Experimental techniques
1.1. Nuclear Magnetic Resonance spectroscopy of heteronuclei
1.2. Conductometry for the characterization of ionic organometallic compounds
2. Theoretical background
2.1. Fundamentals of wave mechanics for a molecular system
2.2. The Born-Oppenheimer approximation
2.3. The variational principle
2.4. Slater determinants and the associated energy
2.5. The independent particle model and the Hartree-Fock equations
2.6. The limits of the Hartree-Fock approach, correlation energy
2.7. Fundamental ideas of DFT, the Hohenberg-Kohn theorems
2.8. The Kohn-Sham method
2.9. Approximating the exchange-correlation functional
2.10. Empirical dispersion corrections
2.11. Implicit solvation – the PCM model
2.12. Basis set and effective core potentials
3. Selected theoretical tools used in this thesis
3.1. Calculation of thermodynamic functions
3.2. Distortion-interaction analysis
3.3. Population analysis
4. References
CHAPTER II – Multiple Roles of Isocyanides in Palladium-Catalyzed Imidoylative Couplings: A Mechanistic Study
1. Context of the Study
1.1. Introduction
1.2. Early studies on the insertion of isocyanides in the C-Pd bond
1.3. Palladium catalyzed imidoylative couplings
1.4. Earlier mechanistic studies related to palladium-catalyzed imidoylative couplings
2. Results and discussion
2.1. Choice of the model reaction
2.2. Generation of Pd(0) from Pd(II) precursors
2.3. Oxidative addition to isocyanide-ligated palladium(0)
2.4. Characterization of the product of oxidative addition
2.5. Interaction of complex 1 with triphenylphosphine
2.6. Interaction of complex 1 with 1,2-bis-(diphenylphosphino)ethane (dppe)
2.7. C-O bond forming reductive elimination
2.8. Theoretical study of the catalytic cycle
2.9. Theoretical study of the C-O bond forming reductive elimination
3. Conclusions
4. Computational details
5. References
CHAPTER III – Palladium-Catalyzed Reductive Benzofuran Ring-Opening Indole Ring-Closure via β-Phenoxide Elimination
1. Context of the Study
1.1. Palladium-catalyzed reactions involving unfunctionalized heteroarenes
1.2. Palladium-catalyzed direct arylation and dearomative couplings of benzofurans
2. Results and discussion
2.1. First steps
2.2. Optimization of reaction conditions
2.3. Scope of the reaction
2.4. Going beyond the synthesis of indoles
2.5. Mechanistic studies
2.6. Proposed catalytic cycle
3. Conclusions
4. References
CHAPTER IV – Copper-Catalyzed Hydroamination of Allenes: Mechanistic Studies and Methodology Development
1. Context of the Study
1.1. Introduction
1.2. Thermodynamic aspects of the hydroamination of alkenes and allenes
1.3. A survey of the literature on the hydroamination of allenes
2. Results and discussion
2.1. Object of the study
2.2. Nature of the catalytically active species
2.3. Catalytic cycle and the origin of selectivity
2.4. From mechanistic insight to methodology development – hydroamination of allenamides
2.5. Application of the hydroamination to the synthesis of an API – P-3374
2.6. Mechanistic insight into the hydroamination of allenamides
2.7. Extension to allenyl ethers
2.8. Extension to N-allenylazoles
2.9. Mechanistic insight into the copper-catalyzed hydroamination of azoles
2.10. Extension to N-allenylsulfonamides
2.11. Mechanistic aspects of the copper-catalyzed hydroamination of N-allenylsulfonamides
3. Conclusions
4. Computational details
5. Bibliography
General conclusions and perspectives
Experimental sections
1. Experimental section of chapter II
1.1. General remarks
1.2. Synthesis and characterization of organometallic complexes
1.3. Synthesis of reference materials
1.4. X-Ray data for compound 1
References
2. Experimental section of chapter III
2.1. General remarks
2.2. General procedure A – Pd-catalyzed ring-opening of benzofuran derivatives
2.3. Synthesis of starting materials
2.4. General procedure B for the alkylation of compounds S3a-d
2.5. Synthesis of complex
References
3. Experimental section of chapter IV
3.1. General remarks
3.2. General procedure for the hydroamination of N-allenylamides
3.3. Pictet-Spengler-type cyclization of hydroamination products
3.4. Synthesis of substrates for mechanistic studies
3.5. General procedure for the isomerization of N-propargylamides, carbamates and ethers to N-allenylamides carbamates, and ethers
3.6. General procedure for the preparation of N-propargyl amides and carbamates
3.7. Study of the reaction between morpholine and Cu(OTf)2 – identification of the organic products
3.8. Hydroamination of N-allenylazoles
3.9. Synthesis of N-propargyl heteroarenes
3.10. Hydroamination of N-allenylsulfonamides
3.11. Synthesis of N-allenylsulfonamides
3.12. Synthesis of miscellaneous allenes
3.13. Synthesis of miscellaneous starting materials
References
