eBook Comprehensive Chirality, 1st Edition

  • Hisashi Yamamoto
  • Erick Carreira
  • Published By:
  • ISBN-10: 0080951686
  • ISBN-13: 9780080951683
  • DDC: 572.8
  • Grade Level Range: College Freshman - College Senior
  • 5648 Pages | eBook
  • Original Copyright 2013 | Published/Released September 2013
  • This publication's content originally published in print form: 2013
  • Price:  Sign in for price



A complete overview of the chiral field including research relevant to synthesis, analytic chemistry, catalysis and pharmaceuticals.

Table of Contents

Front Cover.
Half Title Page.
Title Page.
Copyright Page.
1: Introduction: The Importance of Chirality in Drugs and Agrochemicals.
2: Importance of Chirality in the Field of Anti-Infective Agents.
3: Chirality in Antibacterial Agents.
4: Diastereomers, Enantiomers and Bioactivity. TMC207: A New Candidate for the Treatment of Tuberculosis.
5: Fluorine in Medicinal Chemistry: Importance of Chirality.
6: Peptides and Chirality Effects on the Conformation and the Synthesis of Medicinally Relevant Peptides.
7: Stereochemical Lability in Drug Molecules: Cases where Chirality may not be Critical for Drug Development.
8: Chirality in Agrochemicals.
9: The Use of New Phosphines as Powerful Tools in Asymmetric Synthesis of Biologically Active Compounds.
10: Chirality and Combinatorial Libraries for Drug Discovery, An Overview.
Half Title Page.
Title Page.
Copyright Page.
1: Introductory Remarks: Chiral Pool Syntheses and Diastereoselective Reactions.
2: General Principles of Diastereoselective Reactions: Rigid Templates.
3: General Principles of Diastereoselective Reactions: Diastereoselectivity via Substrate-Directable Reactions (Internal Delivery) and Heterocyclizations.
4: General Principles of Diastereoselective Reactions: Acyclic Control of Diastereoselectivity.
5: General Principles of Diastereoselective Reactions: Diastereoselective Domino Reactions.
6: Chiral Pool Synthesis: From α-Amino Acids and Derivatives.
7: Chiral Pool Synthesis: Starting from Terpenes.
8: Chiral Pool Synthesis: Chiral Pool Syntheses Starting from Carbohydrates.
9: Chiral Pool Synthesis: Chiral Pool Syntheses from cis-Cyclohexadiene Diols.
10: Chiral Pool Synthesis: Chiral Pool Synthesis from Hydroxy Acids: Lactic Acid, Tartaric Acid, Malic Acid, and 2-Methyl-3-Hydroxypropionic Acid.
11: Chiral Pool Synthesis: Chiral Pool Synthesis from Quinic Acid.
12: Selected Diastereoselective Reactions: Additions of Achiral Carbanions to Chiral Aldehydes and Ketones.
13: Selected Diastereoselective Reactions: Aldoltype Additions.
14: Selected Diastereoselective Reactions: Enolate Alkylation.
15: Selected Diastereoselective Reactions: Substrate Controlled Stereoselective Conjugate Addition Reactions with Organocopper Reagents.
16: Selected Diastereoselective Reactions: Free Radical Additions and Cyclizations.
17: Selected Diastereoselective Reactions: Intramolecular Diels–Alder Reactions.
18: Selected Diastereoselective Reactions: Diastereoselective Intra- and Intermolecular 1,3-Dipolar Cycloadditions in Natural Product Synthesis.
19: Selected Diastereoselective Reactions: Electrocyclizations.
20: Selected Diastereoselective Reactions: Ionic and Zwitterionic Cyclizations.
21: Selected Diastereoselective Reactions: Diastereoface-Differentiating Claisen, Cope, and [2,3]-Wittig Rearrangements in Contemporary Natural Product Synthesis.
22: Selected Diastereoselective Reactions: Heck Type Cyclizations.
23: Selected Diastereoselective Reactions: Gold Catalyzed Cyclizations.
24: Selected Diastereoselective Reactions: C–H Insertions.
Half Title Page.
Title Page.
Copyright Page.
1: Amino Acid Derived Auxiliaries: Amino Acids as Chiral Auxiliaries.
2: Amino Acid Derived Heterocyclic Chiral Auxiliaries: The Use of Oxazolidinones, Oxazolidinethiones, Thiazolidinethiones, and Imidazolidinones.
3: Terpene Derived Auxiliaries: Camphor and Pinene Derived Auxiliaries.
4: Terpene Derived Auxiliaries: Menthol and Pulegone Derived Auxiliaries.
5: Terpene Derived Auxiliaries: Miscellaneous Terpene Derived Auxiliaries.
6: Acetogenin (Polypriopionate) Derived Auxiliaries: Tartaric Acid.
7: Acetogenin (Polypriopionate) Derived Auxillaries: Hydroxyacids.
8: Acetogenin (Polypriopionate) Derived Auxillaries: Hydroxyacid Derivatives.
9: Alkaloid Derived Auxiliaries: Cinchona Alkaloids and Derivatives.
10: Alkaloid-Derived Auxiliaries: Ephedra Alkaloids.
11: Alkaloid Derived Auxiliaries: Miscellaneous Alkaloids.
12: Carbohydrate Derived Auxiliaries: Mono (and Disaccharide) Derivatives.
13: Carbohydrate Derived Auxiliaries: Amino Sugar and Glycosylamine Auxiliaries.
14: Synthetically Derived Chiral Auxiliaries: Uses of Derivatives of Non-Carbohydrate Aldehydes and Ketones in Asymmetric Synthesis.
15: Non-Chiral Pool Derived Synthetic Auxiliaries: Use of C2-Symmetric Chiral Diols.
16: Synthetically Derived Auxiliaries: Amines (Including Diamines), Hydrazines and Hydroxylamines, and Amino Alcohols.
17: Synthetically Derived Auxiliaries: Phosphorus Derivatives.
18: Synthetically Derived Auxiliaries: Sulfur Derivatives (Including Sulfilamines and Sulfoximines).
19: Synthetically Derived Auxiliaries: Organometallic Derivatives (Main Group and Transition Metals).
20: Stoichiometric Auxiliary Ligands for Metals and Main Group Elements: Ligands for Lithium.
21: Stoichiometric Auxiliary Ligands for Metals and Main Group Elements: Ligands for Magnesium and Calcium.
22: Chiral Ligation for Boron and Aluminum in Stoichiometric Asymmetric Synthesis.
23: Stoichiometric Auxiliary Ligands for Metals and Main Group Elements: Ligands for Silicon.
24: Stoichiometric Auxiliary Ligands for Metals and Main Group Elements: Ligands for Tin and Stannanes.
25: Stoichiometric Auxiliary Ligands for Metals and Main Group Elements: Ligands for Zinc.
26: Stoichiometric Auxiliary Ligands for Metals and Main Group Elements: Ligands for Chromium.
27: Stoichiometric Auxiliary Ligands for Metals and Main Group Elements: Ligands for Titanium and Zirconium Complexes.
Half Title Page.
Title Page.
Copyright Page.
1: Introduction: General Concepts.
2: C–C Bond-Forming Reactions via the Heck Reaction.
3: C–C Bond-Forming Reactions via Cross-Coupling.
4: C–C Bond Formation (Metathesis).
5: C–C Bond Formation by Metal-Catalyzed Asymmetric Allylic Alkylation.
6: C–C Bond Formation (Metal-Catalyzed Reductive Aldol Coupling).
7: C–C Bond Formation (Transition Metal-Catalyzed Michael).
8: C–C Bond Formation (Metal-Carbene Catalyzed).
9: C–C Bond Formation Using Lewis Acids and Silicon Enolates.
10: Enantioselective Aldol Reactions Catalyzed by Chiral Lewis Bases.
11: C–C Bond-Forming Reactions via Transmetallation Using Silyl Enol Ethers.
12: Direct C–C Bond Formation (Henry, aza-Henry).
13: Direct C–C Bond Formation (Michael, Aldol, and Mannich).
14: Reactions Using Thioamide and Allylic Cyanide.
15: C–C Bond Formation.
16: Enantioselective Cyanation of Carbonyls and Imines.
17: Asymmetric 1,2-Addition of Organometallics to Carbonyl and Imine Groups.
18: C–C Bond Formation (1,2-Alkenylation).
19: To Catalytic Asymmetric 1,2-Alkynylation.
20: Other C–C Bond Formations Including Au.
Half Title Page.
Title Page.
Copyright Page.
1: Asymmetric Baeyer–Villiger Oxidation.
2: Oxidation: C–O Bond Formation by C–H Activation.
3: Oxidation: Epoxidation (Allylic Alcohol, Homoallylic Alcohol, Simple C=C, Electron Deficient C=C).
4: Oxidation: α-Hydroxylation of Carbonyls.
5: Oxidation: C–N Bond Formation by Oxidation: C–H Bond Activation.
6: Oxidation: C–N Bond Formation by Oxidation (Aziridines).
7: Oxidation: C–N Bond Formation by Oxidation: Dinitrogen Addition to Double Bond (Diamino).
8: Asymmetric S–O Bond Formation by Oxidation.
9: Oxidation: C–X Bond Formation (X=Halogen, S, Se).
10: Reduction – Hydrogenation: C=C; Chemoselective.
11: Reduction – Hydrogenation: C=O; Chemoselective.
12: Asymmetric Hydrogenation of Prochiral C=N Bonds.
13: Reduction: Hydrosilylation.
14: Reduction: Hydroformylation C–H and C–C.
15: Reduction: Hydrocyanation of C=C.
16: Reduction: Enantioselective Hydrovinylation of Alkenes.
17: Reduction: Pinacol Coupling.
18: Addition Reaction: Kinetic Resolution.
19: Addition Reaction: 1,4 Addition Heteroatom.
20: Addition Reaction: Cycloaddition Involving Oxidation (N=N, N=O; No C–C.
21: Desymmetrization of meso Diols.
22: Desymmetrization of meso Epoxide.
23: Desymmetrization of meso Anhydride.
Half Title Page.
Title Page.
Copyright Page.
1: C–C Bond Formation: Alkylation.
2: C–C Bond Formation: Michael Reaction.
3: C–C Bond Formation: Mannich Reaction.
4: C–C Bond Formation: Aldol Reaction with Proline Derivatives.
5: C–C Bond Formation: Aldol Reaction with Non-Proline Derivatives.
6: Henry and aza-Henry Reactions.
7: C–C Bond Formation: Cyanation.
8: Allylations of C–O and C–N Double Bonds and Related Reactions.
9: C–C Bond Formation: (aza) Morita–Baylis–Hillman Reaction.
10: C–C Bond Formation: Diels–Alder Reaction.
11: Cyclopropanation Reactions.
12: Benzoin and Stetter Reactions.
13: C–C Bond Formation: Cascade or Domino Reaction.
14: C–N Bond Formation: α-Amination and α-Hydrazination of Carbonyl Compounds with DEAD and Related Compounds.
15: C–N Bond Formation: Aziridine Formation.
16: C–O Bond Formation: α-Oxygenation.
17: C–O Bond Formation: Acylation of meso Diols.
18: C–O Bond Formation: Desymmetrization of Acid Anhydride.
19: C–O Bond Formation: Epoxide Formation.
20: C–X Bond Formation: α-Halogenation of Carbonyl Compounds.
21: C–X Bond Formation: Organocatalytic Enantioselective Halogenation of meso Epoxides.
22: C–X Bond Formation: Organocatalytic α-Sulfenylation and α-Selenenylation.
23: Oxidation: Organocatalyzed Asymmetric Epoxidation of Alkenes.
24: Oxidation: Epoxidation of Enones.
25: Reduction: Asymmetric Transfer Hydrogenation with Hantzsch Esters.
Half Title Page.
Title Page.
Copyright Page.
1: Introduction and General Concepts.
2: Screening Methods for Enzymes.
3: Directed Evolution and (Semi-) Rational Design Strategies for the Creation of Synthetically Useful, Stereoselective Biocatalysts.
4: Cofactor Recycling for Enzyme Catalyzed Processes.
5: Reaction Engineering of Biotransformations.
6: Hydrolysis and Reverse Hydrolysis: Hydrolysis and Formation of Amides.
7: Hydrolysis and Reverse Hydrolysis: Selective Nitrile Hydrolysis Using Nitrilase and Its Related Enzymes.
8: Hydrolysis and Reverse Hydrolysis: Halohydrin Dehalogenases.
9: Hydrolysis and Reverse Hydrolysis: Dynamic Kinetic Resolution.
10: Reduction: Asymmetric Biocatalytic Reduction of Ketones.
11: Reduction: Enantioselective Bioreduction of C–C Double Bonds.
12: Oxidation: Oxidases.
13: Oxidation: Stereoselective Oxidations with Cytochrome P450 Monooxygenases.
14: Oxidation: Asymmetric Enzymatic Sulfoxidation.
15: Oxidation: Haloperoxidases.
16: C–X Bond Formation: Hydroxynitrile Lyases: From Nature to Application.
17: C–X Bond Formation: C–C Bond Formation Using TDP-Dependent Enzymes.
18: C–X Bond Formation: Transaminases as Chiral Catalysts: Mechanism, Engineering, and Applications.
19: C–X Bond Formation: Enzymatic Enantioselective Decarboxylative Protonation and C–C Bond Formation.
20: Multi-Enzyme Reactions.
21: Enzymatic Carbohydrate Synthesis.
22: Enzyme Catalytic Promiscuity: Expanding the Catalytic Action of Enzymes to New Reactions.
23: New Emerging Reactions.
24: Enantioselective Hybrid Catalysts.
Half Title Page.
Title Page.
Copyright Page.
1: Perspective and Concepts: Chirality in Nineteenth Century Science.
2: Perspective and Concepts: Biomolecular Significance of Homochirality: The Origin of the Homochiral Signature of Life.
3: Perspective and Concepts: Overview of Techniques for Assigning Stereochemistry.
4: Physical Separations: Solid-State Forms and Habits of Chiral Substances.
5: Physical Separations: Chiral Discrimination of Enantiomers by Diastereomeric Complexation with Chiral Host Compounds.
6: Physical Separations: Behavior of Structurally Similar Molecules in the Resolution Processes.
7: Chromatographic Separations and Analysis: Chromatographic Separations and Analysis of Enantiomers.
8: Chromatographic Separations and Analysis: Chiral Ion and Ligand Exchange Stationary Phases.
9: Chromatographic Separations and Analysis: Protein and Glycoprotein Stationary Phases.
10: Chromatographic Separations and Analysis: Cyclodextrin Mediated HPLC, GC and CE Enantiomeric Separations.
11: Chromatographic Separations and Analysis: Cellulose and Polysaccharide Derivatives as Stationary Phases.
12: Chromatographic Separations and Analysis: Macrocyclic Glycopeptide Chiral Stationary Phases.
13: Chromatographic Separations and Analysis: Chiral Crown Ether-Based Chiral Stationary Phases.
14: Chromatographic Separations and Analysis: New Stationary Phases.
15: Chromatographic Separations and Analysis: Diastereomeric Derivatization for Chromatography.
16: Chromatographic Separations and Analysis: Chiral Separations by Thin Layer Chromatography.
17: Chromatographic Separations and Analysis: Chiral Gas Chromatography.
18: Chromatographic Separations and Analysis: Supercritical Fluid Chromatography for Chiral Analysis and Semi-Preparative Purification.
19: Chromatographic Separations and Analysis: Chiral Detectors for Chromatography.
20: Spectroscopic Analysis: Polarized Light and Optics.
21: Spectroscopic Analysis: Polarimetry and Optical Rotatory Dispersion.
22: Spectroscopic Analysis: Electronic Circular Dichroism.
23: Spectroscopic Analysis: Synchrotron Radiation Circular Dichroism.
24: Spectroscopic Analysis: Exciton Circular Dichroism for Chiral Analysis.
25: Spectroscopic Analysis: Vibrational Circular Dichroism.
26: Spectroscopic Analysis: Raman Optical Activity.
27: Spectroscopic Analysis: Ab initio Calculation of Chiroptical Spectra.
28: Spectroscopic Analysis: NMR and Shift Reagents.
29: Spectroscopic Analysis: Diastereomeric Derivatization for Spectroscopy.
30: Spectroscopic Analysis: Chiroptical Sensors.
31: Physical and Spectrometric Analysis: An Overview of Chiral Physical Analysis.
32: Physical and Spectrometric Analysis: Anomalous Scattering Single Crystal X-Ray Diffraction.
33: Physical and Spectrometric Analysis: Absolute Configuration Determination by X-Ray Crystallography.
34: Physical and Spectrometric Analysis: Nano-Detection of Chirality.
Half Title Page.
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1: Introduction to Industrial Applications of Asymmetric Synthesis.
2: Asymmetry in the Plant: Concepts and Principles for the Scale-Up of Asymmetric Organic Reactions.
3: Industrial Applications of Asymmetric Synthesis: Asymmetric Synthesis as an Enabler of Green Chemistry.
4: Industrial Applications of Asymmetric Reduction of C=C Bonds.
5: Industrial Application of the Asymmetric Reduction of C=O and C=N Bonds, Including Enamides and Enamines.
6: Industrial Applications of Asymmetric Oxidations.
7: Industrial Applications of the Jacobsen Hydrolytic Kinetic Resolution Technology.
8: Industrial Applications of Metal–Promoted C–C, C–N, and C–O Asymmetric Bond Formations.
9: Catalyst Recovery and Recycle: Metal Removal Techniques.
10: Industrial Applications of Organocatalysis.
11: Industrial Applications of Biocatalysis: An Overview.
12: Industrial Applications of Biocatalytic Hydrolysis (Esters, Amides, Epoxides, Nitriles) and Biocatalytic Dynamic Kinetic Resolution.
13: Industrially Relevant Enzymatic Reductions.
14: Industrial Applications of Asymmetric Biocatalytic C–C Bond Forming Reactions.
15: Industrial Applications of Asymmetric Synthesis Using Cross-Linked Enzyme Aggregates.
16: Crystallization as a Tool in Industrial Applications of Asymmetric Synthesis.
17: Industrial Applications of Chiral Chromatography.
18: Industrial Applications of Process Analytical Technology to Asymmetric Synthesis.
19: Synthesis of the Leading HCV Protease Inhibitors.