Eliel E.L., Wilen S.H. Topics in Stereochemistry. Volume 19

John Wiley & Sons, Inc., 1989. — 424 p.In this, the nineteenth volume of the series Topics in Stereochemistry, we are pleased to be able to present five chapters with a wide spread of interest, ranging from stereochemical aspects of solid-state nuclear magnetic resonance to the bearing of enzyme stereospecificity on the understanding of processes of evolution.
The first chapter, “Molecular Structure and Carbon-13 Chemical Shielding Tensors Obtained from Nuclear Magnetic Resonance” by Julio C. Facelli and David M. Grant of the University of Utah, deals with the additional chemical and nmr information that can be obtained by measurement of the
anisotropic chemical shifts in solids as compared to the isotropic shifts in liquids and solutions. In the opinion of the editors, the authors have presented the complex subject of shielding tensors, their relation to anisotropic chemical shifts, and the meaning of such shifts in remarkably lucid fashion. We hope and trust that the chapter will enable our readers to obtain a better understanding of solid state nmr and the information that can be derived from it.
The second chapter, "Resolution of Enantiomers via Biocatalysis" by Charles J. Sih and Shih-Hsiung Wu of the University of Wisconsin, deals with kinetic resolution, principally of alcohols, acids, and esters, making use of the generally high substrate stereoselectivity of enzymes. The emphasis is on hydrolytic enzymes: esterases and lipases. The chapter includes a general treatment of the efficacy of enzymatic kinetic resolution in terms of fundamental kinetic parameters.
The third chapter, "Stereospecificity in Enzymology: Its Place in Evolution" by Steven A. Benner, Arthur Glasfeld, and Joseph A. Piccirilli of the Swiss Federal Institute of Technology, Zurich, Switzerland, is quite different in content from most of the other chapters published in this Series. It relates the substrate and product stereoselectivity of enzymes from a variety of different organisms to the evolutionary relationship, if any, between these organisms. It is pointed out that enzyme stereospecificity, considered as an evolutionary trait, may be adaptive, nonadaptive and drifting, or nonadaptive but preserved through “structural coupling” to an adaptive trait, and that comparison of the stereochemistry of functionally related enzymes from different species can be used to establish hypotheses as to which of the three modes above is the one actually operating.
The fourth chapter, "Enantioselective Synthesis of Non-racemic Chiral Molecules on an Industrial Scale" by John W. Scott of Hoffman-La Roche, Inc., draws attention to the fact that, to an increasing extent, the pharmaceutical industry in particular is interested in synthesizing chiral substances in enantiomerically pure form. This can be done in three ways: by resolution, by synthesis from readily available optically active precursors, and by enantioselective synthesis. The author presents in detail six quite variegated examples of enantioselective syntheses that are practiced commercially and for which experimental procedures are available.
The last chapter, “Stereochemistry of the Base-Promoted Michael Addition Reaction” by David A. Oare and Clayton H. Heathcock of the University of California at Berkeley, presents an exhaustive-and as far as we are aware the first-summary of the stereochemical aspects of 1,4-addition of carba-
nionic and similar species to α,β-unsaturated carbonyl and related compounds. In addition to presenting an enormous amount of empirical information painstakingly collected from the literature, the authors have undertaken a classification of the stereochemical aspects of various addition schemes, similar to analogous classifications previously used by Heathcock and others for the aldol condensation. A sequel to this chapter by the same authors, dealing with uncatalyzed Michael reactions of enamines and Lewis acid catalyzed reactions of enol ethers with α,β-unsaturated carbonyl compounds, will appear in the next volume of this Series.
This volume is dedicated to the memory of David A. Ginsburg who passed away, after a long illness, on March 9, 1988. Dave Ginsburg had been an advisor to this Series since its inception in 1967 and, among all our advisors, excelled in the number of constructive suggestions for major topics and authors that he made. Not just one or two, but several chapters that have appeared in this Series resulted from his suggestions. We shall miss him both as one of our most helpful advisors and as a personal friend.