Organometallics in Process Chemistry (Topics in Organometallic Chemistry, 65)

Foreword
Preface
Contents
Editors and Authors
Organometallics in Process Chemistry: An Historical Snapshot
	1 Introduction
	2 Main Group Organometallics as Stoichiometric Reagents
		2.1 Organomagnesium Reagents
		2.2 Organolithium Reagents
	3 Transition Metal Organometallics in Catalysis
		3.1 Hydroformylation
		3.2 Asymmetric Hydrogenation
		3.3 Cross-Coupling
		3.4 Metathesis
		3.5 C-H Activation
	4 Emerging Technologies
		4.1 Photoredox Catalysis
		4.2 Flow Chemistry
		4.3 Ester Hydrogenation Under Greener Conditions
		4.4 Organic Electrosynthesis
		4.5 Computational Modelling for Reaction Predictability
	5 Summary and Outlook
	References
Organometallic Approaches to [3.1.0] Bicycles in Process Chemistry
	1 Introduction
	2 Intermolecular Metallocarbenoid Cyclopropanation
		2.1 Cyclopropanation of Electron-Rich Heterocycles
		2.2 Cyclopropanation of Less Electron-Rich Heterocycles
		2.3 Simmons-Smith Cyclopropanations
	3 Michael-Initiated Ring Closure
		3.1 Reactions Between Sulfur Ylides and Enone Substrates
		3.2 Reactions Between Sulfur Ylides and 1,4-Enedicarbonyl Substrates
		3.3 Reactions Between α-Halo Enolates and 1,4-Enedicarbonyl Substrates
	4 Intramolecular Metallocarbenoid Cyclopropanation
		4.1 α-Diazocarbonyl Substrates
		4.2 Lithium Carbenoids
	5 Nucleophilic Displacement Approaches
		5.1 Cyclization of Enolates
		5.2 Intermolecular Enolate Double Addition to Epichlorohydrin
	6 Conclusion
	References
Structural Diversity in Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation Reactions
	1 Introduction
	2 ATH Catalysts
	3 ATH of Polyfunctionalized Ketones
	4 Diastereoselective TH
	5 ATH of Imines
	6 ATH Through Dynamic Kinetic Resolution (DKR)
	7 Conclusions
	References
Application of Organometallic Catalysts in API Synthesis
	1 Introduction
	2 Asymmetric Hydrogenation
		2.1 α-Amino Acids
		2.2 β-Amino Acids
		2.3 Chiral Carboxylic Acids
		2.4 Chiral Amines
		2.5 Chiral Alcohols
	3 C-H Functionalization
	4 Cyclopropanation
	5 Hydroformylation
	6 Cross-Coupling for the Formation of Carbon-Carbon and Carbon-Heteroatom Bonds
		6.1 Cycloaddition Reaction
	7 Transition Metal-Catalyzed Transformations in Batch and Continuous Mode
	8 Conclusion and Prospect
	References
Process Economics and Atom Economy for Industrial Cross Coupling Applications via LnPd(0)-Based Catalysts
	1 Introduction
		1.1 A Brief Overview of Cross Coupling Technology
	2 Process Drawbacks of In Situ-Generated Palladium Catalysts and Even the Classical Preformed Pd(Ph3P)4
		2.1 Process Drawbacks of Using Pd(OAc)2
		2.2 Process Drawbacks of Pdydbaz
	3 Process Benefits of Preformed Pd Complexes and Catalyst Selection
		3.1 Preformed Catalysts
		3.2 L2Pd(0)
			3.2.1 L2PdX2 Introduction
			3.2.2 L2PdX2 Applications
				Limitations of L2PdX2 Pre-catalysts
			3.2.3 A Special Class of L2Pd(0): Bidentate (L-L)PdX2
				Application of Bidentate (L-L)PdX2
			3.2.4 Special Note on L2PdX2
			3.2.5 L2Pd(0) Pre-catalysts
				Process Applications of L2Pd(0)
				Limitations of L2Pd(0)
		3.3 L1Pd(0) Pre-catalysts
			3.3.1 Development of L1Pd(0) Buchwald Palladacycle Pre-catalysts
				Application of Buchwald Palladacycles
				Process Drawbacks of Buchwald Palladacycles
			3.3.2 Development of L1Pd(0) π-Allyl Pre-catalysts
				Process Applications of L1Pd(0) Allyl/Crotyl Pd
				Overcoming Process Drawbacks of π-Allyl Pre-catalysts
	4 Conclusion
	References
Organometallic Processes in Water
	1 Organometallic Processes in Water
	2 Development of Tailor-Made Catalysts for Surfactant Chemistry and Their Applications to Reductions and Cross-Coupling Transf...
	3 Applications to Multistep and Telescoped Sequences
	References
Meeting Metal Limits in Pharmaceutical Processes
	1 Introduction
		1.1 Understanding and Optimising the Metal-Catalysed Process
		1.2 Heterogeneous Catalysis
	2 Methods of Removal
		2.1 Extraction and Precipitation Treatments and Associated Problems
			2.1.1 Chromatography
			2.1.2 Crystallisation
			2.1.3 Precipitation of Catalyst Residues
			2.1.4 Extraction
			2.1.5 Distillation
		2.2 Adsorption and Filtration Methods
			2.2.1 Activated Carbon
			2.2.2 Nanofiltration
			2.2.3 Metal Scavengers
				Silica-Based Metal Scavengers
				Organic Polymers
			2.2.4 Towards a Cost-Effective Strategy for Metal Removal
				Screening
				Optimisation: Isotherms
				Optimisation: Kinetics
				Slurry or Fixed-Bed Trial
			2.2.5 Using DoE as an Optimisation Tool
	3 Analysis
	4 Case Studies
		4.1 Applying Metal Scavengers at the Pilot Plant Scale
			4.1.1 Removal in Batch Mode
			4.1.2 Early Developments in the Use of Scavenging Technology
			4.1.3 Development of a Cartridge-Based Scavenging System
			4.1.4 Development and Optimisation of Single-Pass Cartridge Scavenging
		4.2 Batch Versus Fixed-Bed Removal: A Cost Analysis
		4.3 Replacing Carbon with a Metal Scavenger
		4.4 Use of a Metal Scavenger in Acidic Solutions
		4.5 Processes Which Require Multiple Metal Removal Techniques
		4.6 Ruthenium Removal Using a Metal Scavenger
		4.7 Removing Multiple Metals with One Scavenger
		4.8 Adsorbent Screening for Removal of Coloured Impurities
	5 Conclusion
	References
Sodium Acrylate from Ethylene and CO2: The Path from Basic Research to a System Appropriate for a Continuous Process
	1 Introduction
	2 Catalysts
	3 Bases
	4 Solvents
	5 Process Concepts
	6 Conclusion
	References
Oxygen Effect in Heteromultimetallic Catalysis: Oxygen-Bridged Catalysts for Olefin Polymerization Process
	1 Introduction
	2 Conceptual Background: Effect of Oxygen on the Active Metal Center
	3 Introducing the Oxygen Between Two Metal Centers: Development of M-O-M′ Containing Molecular Catalysts
		3.1 Synthesis of Precursors for Heterometallic Complexes: Main-Group and Transition Metal Hydroxides
			3.1.1 Aluminum Hydroxides
			3.1.2 Zirconium Hydroxide
		3.2 Synthetic Methodology for Construction of MOM′ Motif
		3.3 Synthetic Strategy of Inserting a Lewis Acid Between Active Metal Centers
			3.3.1 Metallocene-Nonmetallocene Heterobimetallic Complexes: Group-4 Metallocenes Grafted on Aluminum Oxide
			3.3.2 Half-Metallocene Group-4 Metal Precursors Grafted on Aluminum Oxide
			3.3.3 Heterometallic Oxides of Aluminum and Non-metallocene Group-4 Metal Precursors
		3.4 Ethylene Polymerization Using Lewis Acid Grafted Heterometallic Catalysts
			3.4.1 Polymerization Data Analysis
			3.4.2 Structure and Activity Relationship
		3.5 Hetero Transition Metals: Assembly and Development of Bimodal Catalyst
		3.6 Study of the Catalytically Active Species
		3.7 Investigations of Styrene Polymerization
	4 Oxygen Effect on the Catalytic Activity
	5 Conclusions
	References
Correction to: Organometallics in Process Chemistry: An Historical Snapshot
	Correction to: Chapter ``Organometallics in Process Chemistry: An Historical Snapshot´´ in: V. Sivakumar et al., Topics in Org...
Index