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Edited by

László Poppe and Mihály Nógrádi


Contributing Authors

László Poppe, József Nagy, Gábor Hornyánszky and Zoltán Boros


Stereochemistry and Stereoselective Synthesis

An Introduction




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Nowadays, the development of molecular sciences brings about a revolutionary change of our world, life, and culture as once did the industrial revolution laying the foundations of our modern world. This molecular revolution, one of the milestones of which was the elucidation of the structure of the hitherto largest known natural compound, the human genome, extends in a dimension hitherto unheard of our knowledge of both ourselves and the universe. A key element of this molecular revolution is chemistry, and within it organic chemistry, contributing a lion's share in the twentieth and twenty-first centuries to the significant achievements of biology, medical, material, and environment sciences.

Similar to other sciences, organic chemistry plays a key role in our knowledge of the universe, and within chemistry a special place is allotted to the study of organic molecules. Apart from the potential of synthetic organic chemistry to construct molecules to be found in nature, it is capable to construct molecules not produced in nature.

A key problem of organic synthesis is selectivity, and within this domain stereoselectivity, a capacity to prepare selectively just one of the possible stereoisomeric structures. The importance of stereochemistry has been recognized in the very early period of organic chemistry: J. B. Biot observed in 1815 that certain organic compounds and their solutions rotate the plane of planar polarized light. L. Pasteur (1948) separated (resolved) the optically inactive tartaric acid to two optically active forms and made one of the most important hypotheses in stereochemistry, namely that the two forms are related as mirror images. J. A. LeBel and J. J. van't Hoff (1874) recognized the tetrahedral bond structure of carbon and that this structure enables, in the case of four different ligands, the existence of two nonidentical mirror image structures (enantiomers). H. E. Fischer after having identified and synthesized most of the 16 possible stereoisomeric forms of aldohexoses (1891) suggested a representation of three-dimensional structures in two dimensions, while M. A. Rosanoff (1905) proposed the conventional absolute configuration of d-(+)-glyceraldehyde.

Stereochemistry and stereoselective synthesis received a significant impetus in the middle of the past century when J. M. Bijvoet (1951) determined the actual absolute configuration of (+)-tartaric sodium rubidium salt with the aid of anomalous scattering in X-ray diffraction.

The relevance of stereochemical studies was recognized by awarding a series of Nobel Prizes. The foundation of modern stereochemistry was laid down in the monograph of M. S. Newman (1956). D. H. R. Barton and O. Hassel were awarded the Nobel Prize (1969) for conformational studies, while V. Prelog and J. W. Cornforth (1975) for analyzing the stereochemistry of enzyme-catalyzed reactions. Nobel-Prize-winning studies were carried out by D. J. Cram, J. M. Lehn, and C. J. Pedersen (1987) of selective interactions in supramolecular systems; W. S. Knowles, R. Noyori, and B. Sharpless (2001) for elaborating stereoselective synthetic methods.

The practical importance of stereochemistry is accentuated by the fact that nowadays almost exclusively enantiopure drugs can be registered and the inactive enantiomers are regarded as “contaminants.” It is therefore not surprising that manufacturing enantiopure compounds is a multibillion dollar business increasing about 10% per year. Accordingly, development of stereoselective methodology of manufacturing and analyzing pure enantiomers is becoming a central issue for the pharmaceutical, pesticide, cosmetic, and even of household chemical industry.

To write a textbook on any field of science is always challenging, especially about stereochemistry and stereoselective methodology, which is now in extremely fast development. The present work is intended to serve not only students of chemistry but also a wider circle of readers, namely to those whose main interest is outside stereochemistry or even organic chemistry, but who wish to have an overview about the problems, the scope, and potentials of this highly interesting field of chemistry. We hope to find among our potential readers biochemists, polymer chemists, pharmacologists, pharmacists, biologists, and workers in other branches of biosciences.

Part I
Basic Concepts at the Molecular Level

The inherent difficulty of correlating structure with properties is that structure is a concept at the molecular (microscopic) level, while properties are in general “macroscopic” manifestations. Difficulties of comparing the two levels can be attributed to two factors: the quantity of material and the time required for the determination of properties.

This part deals with the basic concepts of stereochemistry focusing at the molecular (microscopic) level.