Metallocenes in Regio- and Stereoselective Synthesis

✍ Scribed by Hapke M., Kotora M. (ed.)

• Publisher: Springer
• Year: 2024
• Tongue: English
• Leaves: 212
• Series: Topics in Organometallic Chemistry
• Category: Library

✦ Synopsis

This book presents the latest synthetic protocols for the assembly of functionalized Cp ligands and their transition metal complexes. Cyclopentadienyl (Cp) complexes of transition metals belong to the most important classes of transition metal complexes with tightly bound ligands in the coordination sphere since their discovery in the middle of the last century. Even though they have been known for a long time, this field constantly evolves to deliver novel modified Cp ligands and complexes and to blossom into new fields of application. Beside the synthesis of ligands and metal complexes this book concentrates on novel and prospering fields of their application in organic synthesis. In this respect the Cp complexes have been applied to induce and catalyze various significant chemical transformations such as new C-C bond formation involving unsaturated substrates (e.g. cyclotrimerizations, cycloadditions, carbometallations, etc.), C-H bond and C-C bond activations followed by subsequent reactions (e.g. arylation, alkenylations, annulations, etc.), as well as many other processes. This volume also covers the recent development and application of chiral Cp complexes in enantioselective synthesis.

✦ Table of Contents

Cover
Topics in Organometallic Chemistry Series: Volume 74
Aims and Scope
Metallocenes in Regio- and Stereoselective Synthesis
Copyright
Preface
Contents
Synthesis and Application of Highly Substituted Cyclopentadienes
1. Introduction
2. Synthesis of Highly Substituted Cyclopentadienes and Pentafulvenes
2.1 Alkyl- and Aryl-Substituted Cyclopentadienes
2.2 Functionalized Cyclopentadienes
2.3 Pentafulvenes
3. Application to Synthesis of Half-Sandwich Metallocenes of Late Transition Metals
3.1 From Highly Substituted Cyclopentadienes
3.2 From Highly Substituted Pentafulvenes
4. Summary and Outlook
References
Synthesis of 1,2-Disubstituted Cyclopentadienes and Their Application
1. Introduction
2. 1,2-Disubstituted Cyclopentadienes
3. General Synthetic Approaches to 1,2-Dihomo and 1,2-Diheterosubstituted Cyclopentadienes
3.1 Regioselective Synthesis Based on Pauson-Khand Reaction
3.2 Regioselective Synthesis Based on Retro-Diels-Alder Reaction
3.3 Regioselective Synthesis Based on Haloallylation of Alkynes
3.4 Regioselective Synthesis Based on Alkylation of 2-Substituted 2-Cyclopentenones
4. Specific Synthetic Approaches to 1,2-Dialkylatedcyclopentadienes
4.1 Alkylation of Cyclopentadiene
4.2 Rearrangements
4.3 Pyrolysis
4.4 Insertion of CO into Transition Metal Complexes
5. Specific Synthetic Approaches to 1,2-Diarylated Cyclopentadienes
6. Complexes Bearing 1,2-Disubstituted Cyclopentadienes (Prepared from the Corresponding Cyclopentadienyl Salts)
6.1 Titanocenes
6.2 Zirconocenes
6.3 Manganocenes
6.4 Rhenocenes
6.5 Ferrocenes
6.6 Ruthenocenes
6.7 Rhodocenes
6.8 Other Methods for Preparation of 1,2-Disubstituted Cyclopentadienyl Sandwich Complexes
6.9 X-Ray Diffraction Analyses
7. Conclusion and Outlook
References
Synthesis and Application of Novel Chiral Cp Ligands in Transition Metal Catalysis
1. Introduction
2. Short History of Chiral Cp Ligands
3. Synthesis of Ligands and Complexes with C2 Symmetry and Their Application
3.1 Mannitol-Based Ligands
3.2 StreptavidinBiotin-Cp-Based Ligand
3.3 Binaphthyl-Based Ligands
3.4 BINOL-Based Ligands
3.5 SPINOL-Based Ligands
3.6 Annelated Cyclopentane-Based Ligands
3.7 Ferrocenyl-Based Ligands
3.8 Bicyclo[2.2.2]Octane-Based Ligands
4. Synthesis of Complexes Without C2 Symmetry and Their Application
4.1 JasCp-Based Catalysts
4.2 Planar-Chiral Cyclopentadienyl or Indenyl Catalysts
4.3 Chiral Indenyl or Related Catalysts
References
Planar Chiral Ferrocenes: A Concise Introduction
References
Knölker-Type Catalysts for (Asymmetric) Hydrogenation Reactions
1. Introduction
2. Historical Background
3. Catalytic Applications of Knölker-Type Complexes
4. Asymmetric (Transfer) Hydrogenations
References
Selective Transformations Mediated by Group 4 Metal Cyclopentadienyl Complexes
1. Introduction
2. Chiral Group 4 Cp Complexes
3. Radical Reactions Mediated by Ti(III) Species
4. Photoredox Catalysis with Group 4 Metallocenes
5. Low-Valent Metallocenes for C-C Bond Forming or Cleavage
6. Reactions Involving Hydrometallation and Related Processes
7. Polymerisation Catalysis
8. Miscellaneous Reactions
References
Naturally Occurring Cyclopentadienes and Cyclopentadienyl Anions
1. Introduction
2. Natural Compounds with Cyclopentadiene or Cyclopentadienyl Anion Scaffold
3. Other Cyclopentadienes
4. Syntheses of Compounds Possessing the Cyclopentadiene Fragment
4.1 Total Syntheses
4.2 Model Studies
5. Summary
References
Naturally Occurring Diazofluorenes
1. Introduction
2. Isolation of Natural Products
2.1 Monomeric Natural Compounds
2.2 Dimeric Compounds
3. Syntheses of Compounds Possessing the Diazocyclopentadiene Fragment
3.1 Synthesis of Monomers
3.1.1 Total Synthesis of Monomers
3.1.2 Model Studies on Monomers
3.2 Synthesis of Dimers
3.2.1 Total Synthesis of Dimers
3.2.2 Model Studies Towards Dimers
4. Summary
4.1 Synthesis Added in Proof (March 2, 2023)
References