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Table of contents
Chapter 1: Pd
Chemistry and Annulation Reactions
1.Palladium catalysis
2. Annulation reactions
2.1 Pioneering works
2.2 Annulation reactions involving Pd chemistry
2.2.1 Bis nucleophile bearing vinyl/aryl halides
2.2.2 Annulations between bis nucleophiles and bis allylic electrophiles
2.2.3 Annulation from Pd TMM or cyclopropanes
2.2.4 Pd catalyzed [3+2] C−C/N−C bond forming annulations base d on C H activation
Chapter 2: Palladium Catalyzed [3+2] C−C/N−C Bond Forming Annulation
1. Conception of the new [3+2] C C/N C annulation plan
2. First studies and optimization of the reaction conditions
3. S cope and limitations of the Pd catalyzed [3+2] annulation
3.1 From resonance stabilized N sulfony l acetamides
3.2 The influence of the substitution at the N position of the N amido ester
3.3 Scope of cyclic α,β unsaturated γ oxycarbonyl derivatives
4. Mechanism
5. Studies of enanti oselectivity
5.1 Concepts in the asymmetric Pd catalyzed allylation
5.2 Pd catalyzed asymmetric [3+2] annulations with chiral phosphine ligands
5.3 Pd catalyzed asymmetric [3+2] annulations with chiral phosphoramidite ligands
6. Conclusion
Chapter 3: Palladium Catalyzed Triple Domino: “ALAMAR” Sequence
1. Introduction
2. Toward a multiple pseudo domino
2.1 The concept
2.2 Th e α arylation of enolizable nucleophiles
2.2.1 Introduction and early studies
2.2.2 The Pd catalyzed intermolecular α arylation of ketones
2.2.3 The Pd catalyzed intramolecular α arylation of ketones
3. Study of the [Allylation / AzaStudy of the [Allylation / Aza–Michael / Arylation] (ALAMAR) Domino sequenceMichael / Arylation] (ALAMAR) Domino sequence
3.1 Preliminary studiePreliminary studiess
3.2 Study of the sequential PdStudy of the sequential Pd–catalyzed [3+2] annulation / arylation from 1s and 2acatalyzed [3+2] annulation / arylation from 1s and 2a
3.3 Study of the ALAMAR domino sequence from 1s and 2aStudy of the ALAMAR domino sequence from 1s and 2a
3.4 Scope of the oneScope of the one–pot domino sequencepot domino sequence
3.5 MechanismMechanism
3.6 Conclusion and PerspectivesConclusion and Perspectives
Chapter 4: Palladium–Catalyzed [3+2]Catalyzed [3+2]–C−C/O−C and C−C/C−C BondC−C/O−C and C−C/C−C Bond–Forming AnnulationForming Annulation
1. Introduction and ObjectivesIntroduction and Objectives
2. Studies of PdStudies of Pd–catalyzed [3+2] annulation betweecatalyzed [3+2] annulation between 3n 3–oxoglutarate and 2oxoglutarate and 2–cyclohexenone 4cyclohexenone 4–benzoate
2.1 Optimization of the Optimization of the [3+2][3+2]–C−C/O−C annulationC−C/O−C annulation
2.2 Scope and limitations of the PdScope and limitations of the Pd–catalyzed [3+2] annulationcatalyzed [3+2] annulation
2.2.1 PdPd–catalyzed [3+2]catalyzed [3+2]–C−C/O−C annulationsC−C/O−C annulations
2.2.2 PdPd–catalyzed [3+2]catalyzed [3+2]–C−C/C−C annulationsC−C/C−C annulations
2.2.3 PdPd–catalyzed [3+2] annulation between 2a and 1,3catalyzed [3+2] annulation between 2a and 1,3–activated propanactivated propan–22–ones bisones bis–nucleophiles other than
2.2.4 PdPd–catalyzed [3+2] annulation of 2a and biscatalyzed [3+2] annulation of 2a and bis–nucleophiles 19nucleophiles
2.3 MechanismMechanism
3. Conclusion and PeConclusion and Perspectivesrspectives
General Conclusion
Experimental Section
1. General remarksGeneral remarks
2. General proceduresGeneral procedures
2.1 SyntheSynthesis of starting materialssis of starting materials
2.1.1 Synthesis of bisSynthesis of bis–nucleophiles 1nucleophiles 1
2.1.2 Synthesis of bisSynthesis of bis–electrophiles 2electrophiles 2
2.2 Procedures of Procedures of Pd(0)Pd(0)–catalyzed [ 3 + 2 ]catalyzed [ 3 + 2 ]–C−C/N−C bondC−C/N−C bond–forming annulationforming annulation
2.3 Procedures of PdProcedures of Pd(0)(0)–catalyzed triple domino reactionscatalyzed triple domino reactions
2.3.1 Synthesis of tricyclic Synthesis of tricyclic silyl ether silyl ether productsproducts
2.3.2 Synthesis of tricyclic productsSynthesis of tricyclic products
2.4 Procedures of PdProcedures of Pd(0)(0)–catalyzed [3+2]catalyzed [3+2]–C−C/C−C/OO−−CC or or C−C/C−C/CC−−C bondC bond–forming annulationforming annulation 123123
2.4.1 Procedures of PdProcedures of Pd(0)(0)–catalyzed [3+2catalyzed [3+2]]–C−C/C−C/OO−−C bondC bond–forming annulationforming annulation
2.4.2 Procedures of PdProcedures of Pd(0)(0)–catalyzed [3+2]catalyzed [3+2]–C−C/C−C/CC−−C bondC bond–forming annulationforming annulation
3. Analytical dataAnalytical data
3.1 Analytical data of bisAnalytical data of bis–nucleophilesnucleophiles
3.2 Analytical data of bisAnalytical data of bis–electrophileselectrophiles
3.4 Chiral HPLC Chromatograms of compounds relating to Chapter 2Chiral HPLC Chromatograms of compounds relating to Chapter 2
3.5 Analytical data of compounds relating to Chapter Analytical data of compounds relating to Chapter 33
3.6 Analytical data of compounds relAnalytical data of compounds relating to Chapter ating to Chapter 4



