Sustainable Organic Synthesis: Tools and Strategies

Cover
Sustainable Organic Synthesis: Tools and Strategies
Preface
Biographies
Contents
Section 1 - Activation of Chemical Substrates under Sustainable Conditions
Chapter 1 - Assessing the Sustainability of Syntheses of the Anti- tuberculosis Pharmaceutical Pretomanid by Green Metrics
1.1 Introduction
1.2 Syntheses of Pretomanid
1.3 Sustainability Index
1.4 Ranking Analysis of the Pretomanid Synthesis Plans
1.5 Conclusion
References
Chapter 2 - Homogeneous Catalysis
2.1 Introduction
2.2 Catalysis
2.3 Homogeneous Catalysis
2.4 Model Examples
2.4.1 Hydrogenation Reactions
2.4.2 C–C Bond Forming Reactions
2.4.3 C–Heteroatom Bond Forming Reactions
2.4.4 Polymerisation Reactions
2.5 Conclusions
References
Chapter 3 - Heterogeneous Catalysis
3.1 Basic Concepts from a Historical Perspective
3.1.1 Heterogeneous Catalysts
3.1.1.1 Bulk Inorganic Catalysts
3.1.1.2 Bulk Organic Catalysts
3.1.1.3 Supported Catalysts
3.1.2 Heterogeneity Test
3.1.2.1 Recycling Test
3.1.3 Examples of the Application of Heterogeneous Catalysis
3.1.3.1 Lewis Acid- supported Catalysts: A3/KA2 Coupling and Nitro- Mannich Reactions
3.1.3.2 Heteropolyacid- supported Catalysts: Aza- Friedel- Crafts Reaction
3.2 Conclusions
References
Chapter 4 - Biocatalysis, an Introduction. Exploiting Enzymes as Green Catalysts in the Synthesis of Chemicals and Drugs
4.1 Introduction
4.2 Lipases
4.2.1 Lipase- catalysed Hydrolysis of Esters
4.2.2 Lipase- catalysed Esterification Reactions
4.2.3 Lipase- catalysed Aminolysis Reactions
4.2.4 Lipase- catalysed Oxidation Reactions
4.3 Nitrilases
4.4 Monoamine Oxidases (MAOs)
4.5 Ketoreductases (KRED)
4.6 Monooxygenases and Baeyer–Villiger Monooxygenases (BVMO)
4.7 Transaminases
4.8 Other Enzymes and Perspectives
List of Abbreviations
References
Chapter 5 - Activation of Chemical Substrates Under Sustainable Conditions: Electrochemistry and Electrocatalysis
5.1 Introduction
5.2 Principles of Synthetic Organic Electrochemistry
5.2.1 General Setup
5.2.2 Potential vs. Current
5.2.2.1 Potentiostatic Conditions
5.2.2.2 Galvanostatic Conditions
5.2.3 Reaction Setup
5.2.3.1 Power Supply
5.2.3.2 Reaction Vessels
5.2.3.3 Electrodes
5.2.3.4 Solvents
5.2.3.5 Supporting Electrolytes
5.2.3.6 Modes of Electron Transfer
5.3 Application of Electrochemical Procedures for Sustainable Activation of Substrates
5.3.1 Shono Oxidation
5.3.2 Dehydrogenative Aryl–Aryl Coupling
5.3.3 Electroreductive Difunctionalisation of Alkenes
5.3.4 Electrochemical Birch Reduction
5.4 Conclusion
References
Chapter 6 - Colored Compounds for Eco- sustainable Visible- light Promoted Syntheses
6.1 Introduction
6.2 Classes of Colored Compounds Applied in Photochemical Syntheses
6.2.1 Thioketones
6.2.2 α-­Diketones
6.2.3 Barton Esters
6.2.4 Cyanoarenes
6.2.5 Azoderivatives of Formulae R–N=N–R
6.2.6 4- Substituted- 1,4- dihydropyridines
6.2.7 Other Radical Precursors
6.2.8 Carbene Precursors
6.2.9 Nitrene Precursors
6.3 Conclusions
References
Chapter 7 - Activation of Chemical Substrates Under Sustainable Conditions: Mechanochemistry
7.1 Introduction
7.2 Methodology in Mechanochemistry
7.2.1 Laboratory Instrumentation
7.2.2 Sample Preparation
7.2.3 Control of Solid- State Reactivity
7.2.3.1 Liquid- Assisted Grinding (LAG)
7.2.3.2 Ion- and Liquid- Assisted Grinding (ILAG)
7.2.3.3 Polymer- Assisted Grinding (POLAG)
7.2.3.4 Ionic Liquid- Assisted Grinding (IL- AG)
7.2.3.5 Liquid- Assisted Resonant Acoustic Mixing (LA- RAM)
7.3 Analysis of Mechanochemical Reactions
7.3.1 Powder X- Ray Diffraction
7.3.2 Raman Spectroscopy
7.3.3 TRIS- XANES and Solid- State NMR
7.3.4 Temperature Measurement during Milling
7.4 Organic Synthesis Under Mechanochemical Conditions
7.4.1 Metal Catalysis
7.4.2 Organocatalysis
7.4.3 Photocatalysis
References
Chapter 8 - Sustainable Activation of Chemical Substrates Under Sonochemical Conditions
8.1 Introduction
8.2 Sonochemistry, a Chemistry based on Power Ultrasound
8.2.1 Acoustic Cavitation and Associated Effects
8.2.2 Ultrasonic Parameters and Experimental Factors Affecting Cavitation
8.2.2.1 Ultrasonic Frequency
8.2.2.2 Dissipated Ultrasonic Power
8.2.2.3 Hydrostatic Pressure
8.2.2.4 Temperature
8.2.2.5 Nature of the Solvent
8.2.2.6 Dissolved Gas
8.2.2.7 External Pressure
8.2.2.8 Ultrasonic Intensity
8.2.3 Mode of Irradiation and Sonoreactors
8.2.3.1 Modes of Irradiation
8.2.3.2 Equipment
8.2.3.3 Characterization of the Ultrasonic Parameters
8.3 Organic Sonochemistry: beneficial Effects and New Reactivities
8.3.1 Green Organic Sonochemistry
8.3.2 Cases Studies in Organic Sonochemistry
8.3.2.1 Examples of Oxidation Reactions
8.3.2.2 Examples of Reduction Reactions
8.3.2.3 Examples of Fused Heterocycles
8.3.2.4 Examples of Organometallic Reactions
8.3.3 Scale- up and Industrial Applications
8.4 Conclusions: from the Challenges to New Perspectives of Organic Sonochemistry
List of Abbreviations
References
Section 2 - Benign Media for Organic Synthesis
Chapter 9 - Biomass- derived Solvents
9.1 Introduction
9.2 Methyltetrahydrofuran (2- MeTHF)
9.2.1 2- MeTHF as a Solvent in Organic Chemistry Reactions
9.2.2 2- MeTHF as a Solvent in Biotransformations
9.3 Gamma- Valerolactone (GVL)
9.3.1 GVL as a Solvent in Organic Chemistry Reactions
9.3.2 GVL as a Solvent in Biotransformations
9.4 Dihydrolevoglucosenone
9.4.1 Dihydrolevoglucosenone as a Solvent in Organic Chemistry Reactions
9.4.2 Dihydrolevoglucosenone in Biotransformations
9.5 Glycerol and Glycerol- based Solvents (GBs)
9.5.1 Glycerol and Glycerol- based Solvents (GBs) in Organic Chemistry Reactions
9.5.2 Glycerol and Glycerol- based Solvents (GBs) in Biotransformations
References
Chapter 10 - Supercritical Solvents
10.1 Definition of Supercritical State
10.2 Properties of Supercritical Fluids as Pure Substances
10.2.1 SCFs in Practice
10.3 Tailoring SCF Properties
10.3.1 Selected Applications of Supercritical Solvents in Organic Synthesis
10.3.2 Olefin Metathesis Using scCO2 as a Solvent
10.3.3 Platform Chemicals from Glucose in SCW
10.3.4 Biodiesel Production in SC- Methanol/Ethanol
10.3.5 The Enzyme- catalyzed Synthesis of Butyl Levulinate from Levulinic Acid and Butanol: Green Metrics Evaluation
References
Chapter 11 - Challenges of Using Fluorous Solvents for Greener Organic Synthesis
11.1 Introduction
11.2 Perfluorinated Solvents
11.2.1 Physical Properties of Perfluorocarbons and Perfluorinated Polyethers
11.2.2 Organic Synthesis Using Perfluorinated Solvents
11.3 Fluorous- organic Hybrid Solvents
11.3.1 Physical Properties of Fluorous- organic Hybrid Solvents
11.3.2 Organic Synthesis Using Fluorous- organic Hybrid Solvents
11.4 Phase- vanishing (PV) Methods Using a Fluorous Solvent as a Liquid- phase Membrane
11.4.1 Concept of PV Methods
11.4.2 PV Method Accompanied by Photo Irradiation
11.4.3 Grignard- type Reaction Using the PV Method
11.4.4 PV Method Accompanied by in situ Gas Evolution
11.5 Conclusions
References
Chapter 12 - Ionic Liquids and Deep Eutectic Solvents
12.1 A Very Short Introduction
12.2 Ionic Liquids
12.2.1 Ionic Liquid Structure, Synthesis and Basic Properties: A Brief Survey
12.2.2 Sustainable Physical Properties
12.2.3 Solvent Intrinsic Catalysis
12.2.4 Ionic Liquids as a Nice Environment for Metal- based Catalysts
12.2.5 How Sustainable are ILs
12.3 Deep Eutectic Solvents
12.3.1 Deep Eutectic Solvents (DESs): General Overview
12.3.2 Preparation of DESs and Overview of their Properties and Applications
12.3.3 DESs in Organic Synthesis
12.3.3.1 Consecutive Reactions in DESs
12.3.3.2 Unveiling the Role Played by the DES
12.3.3.3 The Case of Reactive DESs
12.3.3.4 Grignard and Organolithium Chemistry in DESs
12.3.3.5 To What Extent are the Green Metrics of Reactions in DESs Investigated
12.3.4 Future Perspective
12.4 Author Credits
References
Chapter 13 - Environmentally Benign Media: Water, AOS, and Water/Organic Solvent Azeotropic Mixtures
13.1 Introduction
13.2 Water and Biphasic/Azeotropic Mixtures as Reaction Solvents
13.2.1 Organic Synthesis Exclusively Performed in Water
13.2.2 Organic Reactions in Aqueous Organic Solvents or a Biphasic System
13.3 Surfactants as an Additive for Chemistry in Water
13.3.1 Anionic Surfactants
13.3.2 Amphiphilic Surfactants
13.4 Use of Aqueous Reaction Media for Industrial Applications
13.5 Academic Incorporation of Chemistry in Water
13.6 Conclusion
References
Chapter 14 - Solvent- free Conditions
14.1 Introduction
14.2 Solvent- free Organic Reactions
14.2.1 Neat Reactions
14.2.2 MOF- catalysed Reactions
14.3 Solid- state Reactions
14.3.1 Thermal Solid- state Reactions
14.3.2 Topochemical Reactions
14.3.3 Solid- state Melt Reactions
14.3.4 Mechanochemical Reactions
14.3.5 Photochemical Reactions
14.4 Asymmetric Reactions
14.5 Continuous Flow Twin- Screw Extrusion
14.6 Conclusion
References
Section 3 - Sustainable Approaches in Organic Synthesis
Chapter 15 - Biomass- derived Platform Chemicals
15.1 The Platform Molecules
15.2 Rich Diversity Across the Platforms
15.3 Heteroatom Content
15.4 Functional Groups/Level of Functionality
15.5 The Challenge of Hydrophobic Platform Molecules
15.6 Time for a New Top Twelve
References
Chapter 16 - Sustainable Tools for Flow Chemistry
16.1 Introduction
16.1.1 Flow Chemistry as a Key Tool in Green and Sustainable Chemistry
16.2 Heterogeneous and Recyclable Catalytic Systems
16.2.1 Pd/C Catalyzed Arylation of Indoles in a Recoverable Polarclean/Water Mixture as the Reaction Medium
16.2.2 Heterogenized Palladium- based Catalytic Systems
16.2.3 Polymer- supported Catalytic Systems
16.3 Selection of Safer and Recoverable Reaction Media
16.3.1 Biomass- derived Solvents
16.3.1.1 Heck–Mizoroki Cross- coupling in GVL
16.3.1.2 Fujiwara–Moritani C–H Alkenylation in GVL
16.3.2 Recoverable Azeotropic Reaction Media
16.3.2.1 Waste Minimized Reduction of Nitrocompounds by a Heterogenous Au- based Catalyst in an EtOH/Water Azeotrope
16.3.2.2 Waste Minimized Ullmann- type Reaction in Biomass Derived Furfuryl Alcohol/Water Azeotrope
16.4 Adoption of Flow Conditions to Access Sustainable Processes
16.4.1 Waste- minimized Synthesis of Questiomicyn- A and Related Compounds
16.4.2 Sustainable Flow Synthesis of Benzoxazoles by Heterogeneous Manganese- based Systems
16.4.3 Leaching- minimized Flow- assisted Protocol for Mizoroki–Heck Reaction
16.4.4 Continuous Flow Waste Minimized C–H Arylation of 1,2,3- triazoles
16.5 Conclusions
References
Chapter 17 - Step Economy
17.1 Introduction to Step Economy
17.2 Cascade Reactions
17.2.1 Introduction
17.2.2 Trifluoromethylation Reaction
17.2.3 Trifluoromethylthiolation Reaction
17.3 Multicomponent Reactions
17.3.1 Introduction
17.3.2 Construction of Fluorine- Containing Functional Groups Involving Difluorocarbene
17.3.3 Fluorinated Functionalization of Carbon–Carbon Unsaturated Bonds
17.4 Conclusion
List of Abbreviations
References
Chapter 18 - Microwave Irradiation
18.1 Introduction to Microwaves
18.1.1 History and Theory
18.1.2 How Microwaves Enhance Organic Reactions
18.1.3 Non- thermal Effect of Microwaves
18.1.4 Microwave Reactors
18.2 Microwave- assisted Organic Synthesis and Green Chemistry
18.2.1 Energy Efficiency and Microwaves
18.2.2 Solvent- free Reactions
18.2.3 Susceptors
18.2.4 Heterogeneous Catalysis
18.2.5 Green Solvents
18.2.6 Flow Chemistry and Green Scale- up
18.2.7 MW- assisted Reactions and the E- factor
18.2.8 The Setup of a Green MW- assisted Chemistry Process
18.3 Conclusions
References
Chapter 19 - Process Intensification: From Green Chemistry to Continuous Processing
19.1 Process Intensification & Green Approaches to Enable a Better Future
19.2 Process Intensification
19.2.1 General Strategies in PI
19.2.2 Continuous Flow Technology: an Essential Tool for PI
19.3 Benefits and Impact of PI
19.3.1 Business Benefits: Responsive Processing
19.3.1.1 On Processing Flexibility
19.3.1.2 Going from the Lab to Production Scales
19.3.2 Sustainability Impact of PI and Continuous Flow Technology
19.3.2.1 Continuous Technology to Improve PI of HSE Problematic Chemistries
19.3.2.1.1
Lab Miniaturisation for Diazomethane Preparation.One illustrative example of safely handling hazardous material involves the gen...
19.3.2.1.2
Handling Organometallics.The use of organometallics in organic synthesis programs is of fundamental importance for making carbon...
19.3.2.2 Continuous Flow Technology to Improve PI vs. Waste Minimization
19.3.2.3 Continuous Technology to Minimize Energy Needs from Processes
19.3.2.4 Continuous Technology to Minimize Intermediate Inventories by Telescoping Steps
19.3.2.5 Continuous Flow Technology to Facilitate Catalytic Processes
19.3.2.6 Continuous Flow Technology to Improve the Output Quality of Processes
19.4 Current Barriers and Inhibitors Towards PI
References
Chapter 20 - The Contribution of Green Chemistry to Industrial Organic Synthesis
20.1 Green Chemistry: Opportunities and Driving Forces
20.2 Green Solvents as Building Blocks for Sustainable Industrial Synthesis
20.2.1 Supercritical CO2
20.2.2 Ionic Liquids
20.2.3 Bio- based Solvents
20.3 Purification and Wastewater Treatments Under Acoustic and Hydrodynamic Cavitation
20.3.1 Sonocrystallisation
20.3.2 Wastewater Purification
20.4 Innovative Reactors for Smart Chemistry
20.4.1 Photoreactors
20.4.2 Microwave Reactors
20.5 Conclusions
References
Subject Index