1st Edition
Chirality in Natural and Applied Science
336 Pages
100 B/W Illustrations
by
Blackwell
An understanding of chirality is central to the study and application of the molecular sciences. Particularly relevant to the work of pharmaceutical, natural product, organic, and analytical chemists, biochemists, and molecular biologists, Chirality in Natural and Applied Science provides a highly practical overview of the chemical significance of chirality.
Contributions from world-class scientists describe our current understanding of chirality and discuss its significant impact on modern chemistry and molecular science. They explore the origins of chirality, its natural occurrence on a variety of scales, and its current and potential applications in research and industry.
Chirality undoubtedly will remain integral to all of molecular science, and as our knowledge and understanding grow, its importance certainly will increase. Bringing together the insights and experience of scientists who have played influential roles in chirality research, Chirality in Natural and Applied Science helps ensure a thorough understanding of chirality, its importance and its applications.
INTRODUCTION-RETOURNONS À PASTEUR! K. Mislow, Princeton University, USA
PASTEUR ON MOLECULAR HANDEDNESS-AND THE SEQUEL, S.F. Mason, Kings College, London, UK
Pasteur's Optical Resolutions
The Chemical-Physics Background to Pasteur's 1848 Discovery
Molecular Structure Theory and Stereoselective Chiral Synthesis
Chance, Necessity, and Chiral Fields in the Evolution of Biomolecular Homochirality
Parity and its Non-Conservation
THE ORIGIN OF BIOMOLECULAR CHIRALITY, A.J. MacDermott, University of Cambridge, UK
Introduction
Homochirality-A Hallmark of Life
Homochirality-Also a Pre-Condition for Life?
The Need for a Chiral Influence
False Chirality-Magnetic Fields
True Chirality-Circularly Polarized Photons
True Chirality-The w Boson
True Chirality-The z Boson
Amplification Mechanisms
PVEDS of Biomolecules
So was it Really the Weak Force?
Look in Space!
Is the Universe Intrinsically Handed?
CHIRALITY AT THE SUB-MOLECULAR LEVEL: TRUE AND FALSE CHIRALITY, L.D. Barron, University of Glasgow, UK
Introduction
Symmetry Principles
True Chirality
Absolute Asymmetric Synthesis
Chirality and Symmetry Violation
The Mixed-Parity States of a Chiral Molecule
Chirality and Relativity
Chirality in Two Dimensions
Concluding Remarks
THE MOLECULAR BASIS OF CHIRAL RECOGNITION, J. Greer and I.W. Wainer, Abbott Laboratories, Illinois, USA and NIH, Maryland, USA
Introduction
Kinetic and Thermodynamic Aspects of Enzymatic Enantioselectivity
Molecular Chiral Recognition Mechanisms
The N-Dechloroethylation of Ifosfamide Enantiomers
Interaction of Peptides and Larger Molecules with Chiral Biopolymers
Concluding Remarks
CHIRALITY IN DRUG DESIGN AND DEVELOPMENT. D.J. Triggle, University of New York at Buffalo, USA
Introduction
The Stereoselectivity of Drug-Receptor Interactions
Biological Consequences of Stereoselective Drug Action
The Basis of Stereoselectivity
Stereoselectivity of Drug Classes
Regulatory Requirements for Chiral Drugs
Decision Processes
CHIRALITY IN MEDICINAL CHEMISTRY, P.N. Patil and D.D. Miller, Ohio State University, USA and University of Tennessee, Memphis, USA
Historical Aspects
Stereoselectivity of the Biosynthesis of Transmitters and Related Medicinals
Affinity and Intrinsic Activity
Steric Aspects of Drug Action at the Cholinergic Neuroeffector Junction
Steric Aspects of Drug Action at the Noradrenergic and Dopaminergic Neuroeffector Junction
Concluding Remarks
SEPARATION OF CHIRAL COMPOUNDS-FROM CRYSTALLISATION TO CHROMATOGRAPHY, W.J. Lough, University of Sunderland, UK
Crystallisation
Russia, Israel, and NMR
Derivatisation
Commercialised Chiral HPLC
Chiral HPLC Beyond the Eighties
Beyond HPLC
Meeting Unfulfilled Needs?
ELECTRONIC CIRCULAR DICHROISM-FUNDAMENTALS, METHODS AND APPLICATIONS, P. Salvadori, L. Di Bari, and C. Rosini, Universita di Pisa, Italy, Universita di Pisa, Italy and Universita della Basilicata a Potenza, Italy
Introduction
Towards an Understanding of Optical Activity and Related Phenomena
Applications to Structural Chemistry
Conclusions and Future Perspectives
CHIRALITY IN THE NATURAL WORLD: CHEMICAL COMMUNICATIONS, K. Mori, Science University of Tokyo, Japan
Introduction
When was chirality found to be important in chemical communications?
How was the utmost importance of chirality in chemical communications recognized?
Current understanding of the importance of chirality in chemical communications-stereochemistry-bioactivity relationships among pheromones
The practical importance of chirality in pheromone-based pest control
Conclusion
CHIRALITY IN THE NATURAL WORLD-ODOURS AND TASTES, W.A. König, Universität Hamburg, Germany
Introduction
The Influence of Chirality on Biological Activity
The Relationship Between Olfaction and Chemical Structure
The Relationship Between Odour and Taste and Chirality
Enantiomeric Odour Differences and their Quantitative Measurement
Analysis of the confiGuration and Enantiomeric Composition of Volatile Chiral Compounds
Stereochemical Analysis of Odorous Compounds
'Electronic nose', Sensor Technology
Concluding Remarks
CHIRALITY IN THE NATURAL WORLD: LIFE THROUGH THE LOOKING GLASS, C.J. Welch, Merck & Co. New Jersey, USA.
Introduction
Background
Special Problems in the Study of Asymmetric Organisms
The Machinery of Life: Symmetric Organisms from Asymmetric Building Blocks
The Asymmetry of Microorganisms
Asymmetry in the Plant World
Asymmetry of Invertebrates
Asymmetry of Fishes
Asymmetry of Birds
Asymmetry of Reptiles and Amphibians
Asymmetry of Mammals
Asymmetry in Humans
Some Recent Advances in the Developmental Biology of Animal Asymmetry
Behavioural Asymmetry
Summary and Conclusion
CONCLUDING REMARKS-CHIRALITY, CHEMISTRY, THE FUTURE, The Editors
INDEX
PASTEUR ON MOLECULAR HANDEDNESS-AND THE SEQUEL, S.F. Mason, Kings College, London, UK
Pasteur's Optical Resolutions
The Chemical-Physics Background to Pasteur's 1848 Discovery
Molecular Structure Theory and Stereoselective Chiral Synthesis
Chance, Necessity, and Chiral Fields in the Evolution of Biomolecular Homochirality
Parity and its Non-Conservation
THE ORIGIN OF BIOMOLECULAR CHIRALITY, A.J. MacDermott, University of Cambridge, UK
Introduction
Homochirality-A Hallmark of Life
Homochirality-Also a Pre-Condition for Life?
The Need for a Chiral Influence
False Chirality-Magnetic Fields
True Chirality-Circularly Polarized Photons
True Chirality-The w Boson
True Chirality-The z Boson
Amplification Mechanisms
PVEDS of Biomolecules
So was it Really the Weak Force?
Look in Space!
Is the Universe Intrinsically Handed?
CHIRALITY AT THE SUB-MOLECULAR LEVEL: TRUE AND FALSE CHIRALITY, L.D. Barron, University of Glasgow, UK
Introduction
Symmetry Principles
True Chirality
Absolute Asymmetric Synthesis
Chirality and Symmetry Violation
The Mixed-Parity States of a Chiral Molecule
Chirality and Relativity
Chirality in Two Dimensions
Concluding Remarks
THE MOLECULAR BASIS OF CHIRAL RECOGNITION, J. Greer and I.W. Wainer, Abbott Laboratories, Illinois, USA and NIH, Maryland, USA
Introduction
Kinetic and Thermodynamic Aspects of Enzymatic Enantioselectivity
Molecular Chiral Recognition Mechanisms
The N-Dechloroethylation of Ifosfamide Enantiomers
Interaction of Peptides and Larger Molecules with Chiral Biopolymers
Concluding Remarks
CHIRALITY IN DRUG DESIGN AND DEVELOPMENT. D.J. Triggle, University of New York at Buffalo, USA
Introduction
The Stereoselectivity of Drug-Receptor Interactions
Biological Consequences of Stereoselective Drug Action
The Basis of Stereoselectivity
Stereoselectivity of Drug Classes
Regulatory Requirements for Chiral Drugs
Decision Processes
CHIRALITY IN MEDICINAL CHEMISTRY, P.N. Patil and D.D. Miller, Ohio State University, USA and University of Tennessee, Memphis, USA
Historical Aspects
Stereoselectivity of the Biosynthesis of Transmitters and Related Medicinals
Affinity and Intrinsic Activity
Steric Aspects of Drug Action at the Cholinergic Neuroeffector Junction
Steric Aspects of Drug Action at the Noradrenergic and Dopaminergic Neuroeffector Junction
Concluding Remarks
SEPARATION OF CHIRAL COMPOUNDS-FROM CRYSTALLISATION TO CHROMATOGRAPHY, W.J. Lough, University of Sunderland, UK
Crystallisation
Russia, Israel, and NMR
Derivatisation
Commercialised Chiral HPLC
Chiral HPLC Beyond the Eighties
Beyond HPLC
Meeting Unfulfilled Needs?
ELECTRONIC CIRCULAR DICHROISM-FUNDAMENTALS, METHODS AND APPLICATIONS, P. Salvadori, L. Di Bari, and C. Rosini, Universita di Pisa, Italy, Universita di Pisa, Italy and Universita della Basilicata a Potenza, Italy
Introduction
Towards an Understanding of Optical Activity and Related Phenomena
Applications to Structural Chemistry
Conclusions and Future Perspectives
CHIRALITY IN THE NATURAL WORLD: CHEMICAL COMMUNICATIONS, K. Mori, Science University of Tokyo, Japan
Introduction
When was chirality found to be important in chemical communications?
How was the utmost importance of chirality in chemical communications recognized?
Current understanding of the importance of chirality in chemical communications-stereochemistry-bioactivity relationships among pheromones
The practical importance of chirality in pheromone-based pest control
Conclusion
CHIRALITY IN THE NATURAL WORLD-ODOURS AND TASTES, W.A. König, Universität Hamburg, Germany
Introduction
The Influence of Chirality on Biological Activity
The Relationship Between Olfaction and Chemical Structure
The Relationship Between Odour and Taste and Chirality
Enantiomeric Odour Differences and their Quantitative Measurement
Analysis of the confiGuration and Enantiomeric Composition of Volatile Chiral Compounds
Stereochemical Analysis of Odorous Compounds
'Electronic nose', Sensor Technology
Concluding Remarks
CHIRALITY IN THE NATURAL WORLD: LIFE THROUGH THE LOOKING GLASS, C.J. Welch, Merck & Co. New Jersey, USA.
Introduction
Background
Special Problems in the Study of Asymmetric Organisms
The Machinery of Life: Symmetric Organisms from Asymmetric Building Blocks
The Asymmetry of Microorganisms
Asymmetry in the Plant World
Asymmetry of Invertebrates
Asymmetry of Fishes
Asymmetry of Birds
Asymmetry of Reptiles and Amphibians
Asymmetry of Mammals
Asymmetry in Humans
Some Recent Advances in the Developmental Biology of Animal Asymmetry
Behavioural Asymmetry
Summary and Conclusion
CONCLUDING REMARKS-CHIRALITY, CHEMISTRY, THE FUTURE, The Editors
INDEX
Biography
W.J. Lough, I.W. Wainer
