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Stereochemistry of organic compounds
Geochimica
Pergamon
et Cosmochimica
Acta, Vol. 59, No. 9, pp. 1901- 1902, 1995 Copyright 0 1995 Elsevier Science Ltd Printed in the USA. All rights reserved
0016.7037/95 $9.50 + .OO
BOOK REVIEWS
Manual ofMineralogy by C. Klein and C. S. Hurlbut Jr. Wiley, 1993, xii + 681 p., vs $70.95 (ISBN O-471-57452-X).
The chapter on “Physical Properties of Minerals” has been substantially improved over previous editions by showing how color in minerals may be caused by crystal field and charge transfer transitions. The origin of the green color of peridot is discussed in detail. The section on magnetism in minerals has also been expanded. Separate chapters on “X-ray Crystallography” and “Optical Properties of Minerals” take an elementary approach and are essentially unchanged from the previous edition. An entire chapter is devoted to “Mineral Stability Diagrams” where a brief introduction to thermodynamics and phase equilibria of one-, two-, and three-component systems is given. The more complicated diagrams contained in the sections on “Systematic Mineralogy” are discussed here. The presentation is at an elementary level. For example, although the concept of entropy is briefly discussed, a demonstration of the effect of cation ordering on entropy is noticeably lacking. A brief description of configurational entropy and perhaps an example (e.g., cordierite) would permit ordering to further illuminate the discussion of the feldspars and other mineral groups. As in previous editions four chapters are devoted to the systematic descriptions of about 200 minerals. This section has been improved by the addition of about forty new illustrations. Outdated information on interfacial angles, axial ratios, and blowpipe analysis has been eliminated from the mineral descriptions. A chapter on “Mineral Assemblages” helps to prepare the student for courses in petrology and a chapter devoted to “Gem Minerals” ensures that the student will be able to avoid embarrassment at social gatherings when called upon to give impromptu lectures about various items of jewelry. Manual ofMineralogy has evolved into an excellent, comprehensive introduction to the science of mineralogy. Concepts and mineral descriptions are carefully balanced in this single text. Most earth science departments will find Manual of Mineralogy to be pitched at an appropriate introductory level for undergraduates which can then be expanded upon, if necessary, in more advanced courses.
Manual of Mineralogy is a truly comprehensive, introductory mineralogy text appropriate for undergraduates in geological or materials science. Since about half of the book is devoted to a systematic description of approximately 200 minerals, Manual ofMineralogy may also be a welcome addition to the personal library of the solid-state scientist. The twenty-first edition of the Manual of Mineralogy has been significantly expanded and revised relative to the twentieth edition (published in 1985). The section on crystal morphology has been improved so that the student is made familiar with the external symmetry of ideal crystals in preparation for the following chapter, “Internal Order and Symmetry” which gives a logical development of the necessary concepts from space group theory. Diopside, beryl, and diamond are used as excellent examples to relate actual crystal stmchues to the abstract idea of a space group. The chapter on “Crystal Chemistry and Chemical Composition of Minerals” from the previous edition has been split into two separate chapters. The first, on “Crystal Chemistry” begins with a useful review of the periodic table and electronic structure of atoms. In addition to the Bohr model, a new section on the Schrodinger model of the atom has been included. The discussion of “Atomic and Ionic Radii” has been significantly improved, showing how radii are obtained and what they really mean. As in previous editions the usefulness of radius ratios in determining coordination number is oversold. The discussion of Pauhng’s rules has been expanded, particularly the discussion of the electrostatic valence rule, the rule that has been shown to have the most firm basis in quantum theory. In future editions, a section describing how the cohesive energy of crystals may be actually be. computed, at least within the ionic model (e.g., Gordon-Kim models), would introduce the student to the power of modem theoretical methods to probe the structure, properties, and stability of minerals. The next chapter, “Mineral Chemistry,” inchides welcome descriptions of analytical methods such as wet chemical analysis, atomic absorption spectroscopy, X-ray fluorescence, and electron probe microanalysis. The section on blowpipe of previous editions has finally been dropped.
Department of Geological Sciences The Ohio State University Columbus, Ohio 43210, USA
James W. Downs
cellently illustrated with examples. A useful and extensive glossary along with an extensive index are also given. Whilst containing the relevant historical background and information, the book is pitched very much at the level of postgraduate, professional, and research chemists. It is much more than a standard text book and is definitely not a book for chemistry undergraduate students. There are many areas which will test the knowledge of many organic chemists to the limit. Before going into details, there is no doubt that any self-respecting organic chemist should have a copy of this book. I suspect, however, that the content is too detailed and too far removed from the majority of geochemists, although I would recommend that they have access to a copy through their departmental library for consultation concerning any aspect of stereochemistry. The book has been logically divided into fourteen chapters, chapter 12 on “Stereoselective Synthesis” being the contribution by Mander. Chapter 1 is basically an historical introduction to the subject. Chapter 2 focuses on defining the terms structure, constitution, configuration, and conformation. There are brief introductory sections to determining and calculating structures. Molecular models are also considered.
Stereochemistry of Organic Compounds by E. L. Eliel and S. H. Wilen with a contribution by L. N. Mander. Wiley, 1994, 1267p., US $74.95 (ISBN O-47 I-01 670-5). This book follows from the last major treatise in this area of organic chemistry Stereochemistry of Carbon Compounds by E. L. Eliel published over thirty years ago in 1962. Since then there have been major advances in NMR spectroscopy and molecular mechanics, now important tools in the area of molecular configuration and conformation. Furthermore, there have been great strides in the ideas of prostereoisomerism and mathematical descriptions of stereochemistry notably in the application of symmetry concepts. Chromatographic methods have also improved significantly and the need in obtaining pure enantiomers has become even more important in the chemical and pharmaceutical industry and academia. This book is therefore a very timely and important up-to-date publication. The writing style is excellent with additional more detailed, descriptive sections neatly indented and printed in a smaller script within the text. I noted only a few minor typographical errors throughout. The figures are also of the highest quality. References are numerous and each topic is ex1901
1902
Book Reviews
Chapter 3 considers stereoisomers and deals with enantiomers and diastereomers. There is an excellent explanation of the six stereoisomers (three enantiomeric pairs) of 2-bromobutane, even though in practice the preparative chemist only encounters two species (+)-2bromobutane and (- )-2-bromobutane. Chapter 4 focuses on symmetry with particular emphasis on synrmetry elements, symmetry operators, and symmetry point groups. Ihis is one area of chemistry where my knowledge was particularly weak and I found the subject well explained and supported with numerous examples. Configuration is the subject of chapter 5 which begins with the Cahn-IngoldPrelog system for specification of molecular configuration and covers more complex examples such as cyclic components than found in normal text books. The uses and problems of other types of nomenclature are also discussed, e.g. erythro/threo, syn/anti, re/si, etc. Determination of absolute configuration by X-ray crystallography (Bijvoet method) is elegantly treated along with the determination of relative configurations by a wide variety of methods such as X-ray, chemical interconversion& consideration of symmetry properties, and spectroscopic methods (the latter being dealt with in more detail in later chapters). Chapter 5 also deals with the rules of Horeau, Prelog, Cram, and Sharpless. “Properties of stereoisomers” is the title of chapter 6. This chapter will be a real eye opener for many readers. There is a superb section on the properties of racemates and of their enantiomer components. I wonder how many chemically educated people realise that it is frequently possible to fractionate enantiomers by chromatography without resort to chiral stationary or chiral mobile phases? Geochemists may be particularly interested in the, albeit short, section on the origin of enantiomeric homogeneity in nature. The determination of enantiomer and diastereomer composition with extensive sections on NMR and chromatography is also described in chapter 6 and is again well illustrated with examples. Chapter 7 deals with the separation of stereoisomers and covers the topics of resolution and racemization. Separation of enantiomers by crystallization makes interesting reading and discusses crystal picking or triage (i.e., manual sorting), preferential crystallization (i.e., inoculation with one enantiomer or in the presence of additives). and spontaneous resolution. Detailed sections follow on the separation of enantiomers via diastereomers, enantiomeric emichment, large-scale resolution (especially with regard to industrial needs), and kinetic resolutions (e.g., sharpless enantioselective epoxidation of allylic alcohols/kinetic resolution of unreacted starting material). The chapter closes with the topic of racemization and discusses the various processes for bringing about this phenomenon. Of interests to geochemists is the section on the racemization of amino acids and a discussion of the mechanisms thereof in basic and acidic media. There is also reference to the application of amino acid racemization for dating fossils. Chapter 8 focuses on heterotopic ligands and faces and prostereoisomerism and prochirality. Terminology is discussed and the relevance to biological chemistry (pro-R and pro-S) is well illustrated with examples. This is then followed with a detailed section on the uses of NMR in this area. Enzyme-catalysed reactions are also covered in this chapter (e.g., ethanol oxidationlacetaldehyde reduction by NAD+/NADH in the presence of yeast alcohol dehydrogenase; pyruvate reduction by NADH in the presence of alcohol dehydrogenase). Finally, one is treated to pro2-chiral centres (or pro-pro-
chiral centres) and chiral methyl, phosphate, and sulphate groups are considered. In Chapter 9 the nomenclature of alkenes including cumulenes is discussed along with chemical and physical (especially NMR) methods for the determination of the configuration of cis-trans isomers. An interesting section covers interconversion of cis-trans isomers. Chapters 10 and 11 deal with conformation in acyclic and cyclic molecules, respectively. Simple saturated acyclic molecules (e.g., ethane, propane, butane) are covered and an interesting discussion of the origin of the torsional barrier in ethane is provided. There is a detailed section on the conformations of pentane and on the intriguing case of 2$dimethylbutane in which the anti and gauche conformations are nearly of equal enthalpy. The anomeric effect in saturated acyclic molecules with polar substituents or chains is also explained. In addition, chapter 10 discusses the conformations of unsaturated acyclic compounds including C=C and C=O functionalities and 1,3-butadiene. Physical and spectral properties of acyclic diastereomers and conformers are covered in detail. Chapter 11 begins with stereoisomerism and configurational nomenclature of ring compounds and discusses the use of the r prefix. The determination of configuration of substituted ring compounds is considered with particular emphasis on NMR spectroscopy. Other sections are concerned with the stability of cyclic molecules, strain, ease of cyclization as a function of ring size, the Thorpe-Ingold effect, and Baldwin’s rules for ring closure. Very detailed discussions of conformational aspects of six-membered rings are considered with emphasis on cyclohexane (chair, half-chair, twist, and boat forms), monosubstituted cyclohexanes, and di- ‘and poly-substituted cyclohexanes (including the nine 1,2,3,4,5,6-hexahydroxycyclohexanes). Physical properties and reactivity (“steric hindrance” and “steric assistance”) in cyclohexanes are also considered in detail. Following this are sections on sp’ hybridised cyclohexyl systems: cyclohexene, cyclohexene oxide, cyclohexadiene, cyclohexanone (including the anomeric effect), and methylenecyclohexane (including discussions on A ‘J and A ‘,’ strain). I found the latter to be extremely relevant to the results of one of my co-workers on pentacyclic triterpenes. Six-membered saturated heterocycles are also considered in detail including the anomeric effect. Chapter 10 then goes on to consider the chemistry of non six-membered ring compounds and then considers fused, bridged, and caged ring systems. Finally, there are sections on some exotic molecules such as paddlanes, propellanes, catenanes, etc., and cage molecules such as cubane, tetrahedrane, adamantane, buckminsterfullerene, etc. As mentioned earlier, chapter 12 is the contribution from Mander and presents an excellent insight into stereoselective synthesis. Chapter 13 is concerned with chiroptical properties and deals with optical rotary dispersion and circular dichroism. In the final chapter (chapter 14) we are treated to those molecules which are chiral but have no chiral centre (e.g., allenes, alkylidenecycloalkanes, biphenyls, spiranes, etc.). In summary, I found little to fault with this book and believe that it will no doubt prove itself to be a milestone in this fascinating area of organic chemistry. School of Chemistry University of Bristol Cantock’s Close Bristol BS8 ITS, England
Tori-en M. Peakman
Pergamon
et Cosmochimica
Acta, Vol. 59, No. 9, pp. 1901- 1902, 1995 Copyright 0 1995 Elsevier Science Ltd Printed in the USA. All rights reserved
0016.7037/95 $9.50 + .OO
BOOK REVIEWS
Manual ofMineralogy by C. Klein and C. S. Hurlbut Jr. Wiley, 1993, xii + 681 p., vs $70.95 (ISBN O-471-57452-X).
The chapter on “Physical Properties of Minerals” has been substantially improved over previous editions by showing how color in minerals may be caused by crystal field and charge transfer transitions. The origin of the green color of peridot is discussed in detail. The section on magnetism in minerals has also been expanded. Separate chapters on “X-ray Crystallography” and “Optical Properties of Minerals” take an elementary approach and are essentially unchanged from the previous edition. An entire chapter is devoted to “Mineral Stability Diagrams” where a brief introduction to thermodynamics and phase equilibria of one-, two-, and three-component systems is given. The more complicated diagrams contained in the sections on “Systematic Mineralogy” are discussed here. The presentation is at an elementary level. For example, although the concept of entropy is briefly discussed, a demonstration of the effect of cation ordering on entropy is noticeably lacking. A brief description of configurational entropy and perhaps an example (e.g., cordierite) would permit ordering to further illuminate the discussion of the feldspars and other mineral groups. As in previous editions four chapters are devoted to the systematic descriptions of about 200 minerals. This section has been improved by the addition of about forty new illustrations. Outdated information on interfacial angles, axial ratios, and blowpipe analysis has been eliminated from the mineral descriptions. A chapter on “Mineral Assemblages” helps to prepare the student for courses in petrology and a chapter devoted to “Gem Minerals” ensures that the student will be able to avoid embarrassment at social gatherings when called upon to give impromptu lectures about various items of jewelry. Manual ofMineralogy has evolved into an excellent, comprehensive introduction to the science of mineralogy. Concepts and mineral descriptions are carefully balanced in this single text. Most earth science departments will find Manual of Mineralogy to be pitched at an appropriate introductory level for undergraduates which can then be expanded upon, if necessary, in more advanced courses.
Manual of Mineralogy is a truly comprehensive, introductory mineralogy text appropriate for undergraduates in geological or materials science. Since about half of the book is devoted to a systematic description of approximately 200 minerals, Manual ofMineralogy may also be a welcome addition to the personal library of the solid-state scientist. The twenty-first edition of the Manual of Mineralogy has been significantly expanded and revised relative to the twentieth edition (published in 1985). The section on crystal morphology has been improved so that the student is made familiar with the external symmetry of ideal crystals in preparation for the following chapter, “Internal Order and Symmetry” which gives a logical development of the necessary concepts from space group theory. Diopside, beryl, and diamond are used as excellent examples to relate actual crystal stmchues to the abstract idea of a space group. The chapter on “Crystal Chemistry and Chemical Composition of Minerals” from the previous edition has been split into two separate chapters. The first, on “Crystal Chemistry” begins with a useful review of the periodic table and electronic structure of atoms. In addition to the Bohr model, a new section on the Schrodinger model of the atom has been included. The discussion of “Atomic and Ionic Radii” has been significantly improved, showing how radii are obtained and what they really mean. As in previous editions the usefulness of radius ratios in determining coordination number is oversold. The discussion of Pauhng’s rules has been expanded, particularly the discussion of the electrostatic valence rule, the rule that has been shown to have the most firm basis in quantum theory. In future editions, a section describing how the cohesive energy of crystals may be actually be. computed, at least within the ionic model (e.g., Gordon-Kim models), would introduce the student to the power of modem theoretical methods to probe the structure, properties, and stability of minerals. The next chapter, “Mineral Chemistry,” inchides welcome descriptions of analytical methods such as wet chemical analysis, atomic absorption spectroscopy, X-ray fluorescence, and electron probe microanalysis. The section on blowpipe of previous editions has finally been dropped.
Department of Geological Sciences The Ohio State University Columbus, Ohio 43210, USA
James W. Downs
cellently illustrated with examples. A useful and extensive glossary along with an extensive index are also given. Whilst containing the relevant historical background and information, the book is pitched very much at the level of postgraduate, professional, and research chemists. It is much more than a standard text book and is definitely not a book for chemistry undergraduate students. There are many areas which will test the knowledge of many organic chemists to the limit. Before going into details, there is no doubt that any self-respecting organic chemist should have a copy of this book. I suspect, however, that the content is too detailed and too far removed from the majority of geochemists, although I would recommend that they have access to a copy through their departmental library for consultation concerning any aspect of stereochemistry. The book has been logically divided into fourteen chapters, chapter 12 on “Stereoselective Synthesis” being the contribution by Mander. Chapter 1 is basically an historical introduction to the subject. Chapter 2 focuses on defining the terms structure, constitution, configuration, and conformation. There are brief introductory sections to determining and calculating structures. Molecular models are also considered.
Stereochemistry of Organic Compounds by E. L. Eliel and S. H. Wilen with a contribution by L. N. Mander. Wiley, 1994, 1267p., US $74.95 (ISBN O-47 I-01 670-5). This book follows from the last major treatise in this area of organic chemistry Stereochemistry of Carbon Compounds by E. L. Eliel published over thirty years ago in 1962. Since then there have been major advances in NMR spectroscopy and molecular mechanics, now important tools in the area of molecular configuration and conformation. Furthermore, there have been great strides in the ideas of prostereoisomerism and mathematical descriptions of stereochemistry notably in the application of symmetry concepts. Chromatographic methods have also improved significantly and the need in obtaining pure enantiomers has become even more important in the chemical and pharmaceutical industry and academia. This book is therefore a very timely and important up-to-date publication. The writing style is excellent with additional more detailed, descriptive sections neatly indented and printed in a smaller script within the text. I noted only a few minor typographical errors throughout. The figures are also of the highest quality. References are numerous and each topic is ex1901
1902
Book Reviews
Chapter 3 considers stereoisomers and deals with enantiomers and diastereomers. There is an excellent explanation of the six stereoisomers (three enantiomeric pairs) of 2-bromobutane, even though in practice the preparative chemist only encounters two species (+)-2bromobutane and (- )-2-bromobutane. Chapter 4 focuses on symmetry with particular emphasis on synrmetry elements, symmetry operators, and symmetry point groups. Ihis is one area of chemistry where my knowledge was particularly weak and I found the subject well explained and supported with numerous examples. Configuration is the subject of chapter 5 which begins with the Cahn-IngoldPrelog system for specification of molecular configuration and covers more complex examples such as cyclic components than found in normal text books. The uses and problems of other types of nomenclature are also discussed, e.g. erythro/threo, syn/anti, re/si, etc. Determination of absolute configuration by X-ray crystallography (Bijvoet method) is elegantly treated along with the determination of relative configurations by a wide variety of methods such as X-ray, chemical interconversion& consideration of symmetry properties, and spectroscopic methods (the latter being dealt with in more detail in later chapters). Chapter 5 also deals with the rules of Horeau, Prelog, Cram, and Sharpless. “Properties of stereoisomers” is the title of chapter 6. This chapter will be a real eye opener for many readers. There is a superb section on the properties of racemates and of their enantiomer components. I wonder how many chemically educated people realise that it is frequently possible to fractionate enantiomers by chromatography without resort to chiral stationary or chiral mobile phases? Geochemists may be particularly interested in the, albeit short, section on the origin of enantiomeric homogeneity in nature. The determination of enantiomer and diastereomer composition with extensive sections on NMR and chromatography is also described in chapter 6 and is again well illustrated with examples. Chapter 7 deals with the separation of stereoisomers and covers the topics of resolution and racemization. Separation of enantiomers by crystallization makes interesting reading and discusses crystal picking or triage (i.e., manual sorting), preferential crystallization (i.e., inoculation with one enantiomer or in the presence of additives). and spontaneous resolution. Detailed sections follow on the separation of enantiomers via diastereomers, enantiomeric emichment, large-scale resolution (especially with regard to industrial needs), and kinetic resolutions (e.g., sharpless enantioselective epoxidation of allylic alcohols/kinetic resolution of unreacted starting material). The chapter closes with the topic of racemization and discusses the various processes for bringing about this phenomenon. Of interests to geochemists is the section on the racemization of amino acids and a discussion of the mechanisms thereof in basic and acidic media. There is also reference to the application of amino acid racemization for dating fossils. Chapter 8 focuses on heterotopic ligands and faces and prostereoisomerism and prochirality. Terminology is discussed and the relevance to biological chemistry (pro-R and pro-S) is well illustrated with examples. This is then followed with a detailed section on the uses of NMR in this area. Enzyme-catalysed reactions are also covered in this chapter (e.g., ethanol oxidationlacetaldehyde reduction by NAD+/NADH in the presence of yeast alcohol dehydrogenase; pyruvate reduction by NADH in the presence of alcohol dehydrogenase). Finally, one is treated to pro2-chiral centres (or pro-pro-
chiral centres) and chiral methyl, phosphate, and sulphate groups are considered. In Chapter 9 the nomenclature of alkenes including cumulenes is discussed along with chemical and physical (especially NMR) methods for the determination of the configuration of cis-trans isomers. An interesting section covers interconversion of cis-trans isomers. Chapters 10 and 11 deal with conformation in acyclic and cyclic molecules, respectively. Simple saturated acyclic molecules (e.g., ethane, propane, butane) are covered and an interesting discussion of the origin of the torsional barrier in ethane is provided. There is a detailed section on the conformations of pentane and on the intriguing case of 2$dimethylbutane in which the anti and gauche conformations are nearly of equal enthalpy. The anomeric effect in saturated acyclic molecules with polar substituents or chains is also explained. In addition, chapter 10 discusses the conformations of unsaturated acyclic compounds including C=C and C=O functionalities and 1,3-butadiene. Physical and spectral properties of acyclic diastereomers and conformers are covered in detail. Chapter 11 begins with stereoisomerism and configurational nomenclature of ring compounds and discusses the use of the r prefix. The determination of configuration of substituted ring compounds is considered with particular emphasis on NMR spectroscopy. Other sections are concerned with the stability of cyclic molecules, strain, ease of cyclization as a function of ring size, the Thorpe-Ingold effect, and Baldwin’s rules for ring closure. Very detailed discussions of conformational aspects of six-membered rings are considered with emphasis on cyclohexane (chair, half-chair, twist, and boat forms), monosubstituted cyclohexanes, and di- ‘and poly-substituted cyclohexanes (including the nine 1,2,3,4,5,6-hexahydroxycyclohexanes). Physical properties and reactivity (“steric hindrance” and “steric assistance”) in cyclohexanes are also considered in detail. Following this are sections on sp’ hybridised cyclohexyl systems: cyclohexene, cyclohexene oxide, cyclohexadiene, cyclohexanone (including the anomeric effect), and methylenecyclohexane (including discussions on A ‘J and A ‘,’ strain). I found the latter to be extremely relevant to the results of one of my co-workers on pentacyclic triterpenes. Six-membered saturated heterocycles are also considered in detail including the anomeric effect. Chapter 10 then goes on to consider the chemistry of non six-membered ring compounds and then considers fused, bridged, and caged ring systems. Finally, there are sections on some exotic molecules such as paddlanes, propellanes, catenanes, etc., and cage molecules such as cubane, tetrahedrane, adamantane, buckminsterfullerene, etc. As mentioned earlier, chapter 12 is the contribution from Mander and presents an excellent insight into stereoselective synthesis. Chapter 13 is concerned with chiroptical properties and deals with optical rotary dispersion and circular dichroism. In the final chapter (chapter 14) we are treated to those molecules which are chiral but have no chiral centre (e.g., allenes, alkylidenecycloalkanes, biphenyls, spiranes, etc.). In summary, I found little to fault with this book and believe that it will no doubt prove itself to be a milestone in this fascinating area of organic chemistry. School of Chemistry University of Bristol Cantock’s Close Bristol BS8 ITS, England
Tori-en M. Peakman