Total Synthesis of Natural Products: The 'Chiron' Approach

Navigating the Chiral Pool in the Total Synthesis of Complex Terpene Natural Products. Chemical Reviews. Brill, Condakes, Ting, and Maimone. 2017 117 ...
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REVIEWf Asymmetry, and Chirality" (6pp.), in which these three sometimes confused concepts are carefully distinguished; "The Specification of Molecular Configuration" (7 pp.); "The Search for Chiral Centers Other Than Carbon" (13 pp.). (Although most of the hook deals with organic compounds, this chapter considers trivalent and "pentavalent" nitrogen and other heteroatoms); "The Stereochemistry of Trivalent Carbon Species" (6 pp.), dealing with carbonium ions, carbon "free radicals," and carbanions; "Rotational 'Barriers' about Single Bonds and Steric Effects" (11 pp.); "The Stereochemistry of Cyclic Compounds: The Early History" (18 pp.); "The Origins and Development of Conformational Analysis" (17 pp.), including both acyclic and cyclic compounds; "Asymmetric Transformations" (8 pp.); and "Some Recent Developments and Future Expectations" (24 pp.), including work on chemical "curiosities" sueh as cyclophanes, betweenanene, tetrahedrane, h m l e n e , propellanes, hullvalene. eatenanes. earbenium ions. ete. as wcll as l,i&kal &orhemistry. As the chapter headingirhuw, the wrlume gives an excellent survey of the progress of itereochemistrv from its inception to the 1YfiOs. It is n gold mine of facts, both wcll knownand little known. Intended not for rhc professional historian hut for "the chemist, the research worker and the nonsoecialist whouishesto lrring himself up ludaceon the hiumriral barkgnund." it doe* not include reiwences, but names of scientirts and dater of their dimweriec are given in the text a\ well as inn Yhn,nology oi Ewnts and I'ubl~cationsi n the Hi-tor, uf Stercuchemiutw." An important featurkof the book is the inclusion of a large number of photographs and diagrams of historic atomic and molecular models by Dalton, Hofmann, Kekul6, Dewar, KBrner, von Baeyer Patern6, Emil Fischer, and others. A most delightful and unusual appendix (9 pp.) is provided on "Stereochemical Satire," and a 4-page list of supplementary readings, a 5-page glossary, and subject (4 pp.) and name (4 pp.) indices are included. Errors in the hook are virtually nonexistent; the few that I found range from venial (Ernest Mohr for Ernst Mohr, p. 167) t o mortal (G. G. Kauffman far G. B. Kauffman, p. 248). This volume is highly recommended, and chemical educators will find it not only a fascinating story hut also a source of valuable material for classroom use. George B. Kauffman California State University. Fresno Fresno. CA 93740

Transmutation: Natural a n d Artificial Thaddeus J. Trenn, Nobel Prize Topics in Chemistry. Heyden & Son, Ltd.. Philadelphia, PA, 1981. xvi 128 pp. Figures. 14.5 X 22 cm. $29.00 HB and $13.50 PB.

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This slim volume is the third in Heyden's Nobel Prize Topics in Chemistry, a "Series of Historical Monographs on Fundamentals of Chemistry," edited by Johannes W. van Spronsen (The first and second volumes"Inorganic Coordination Compounds," by George B. Kauffman, and "Stereochemistry," A190

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of Chemical Education

hy 0. Bertrand Ramsay-are reviewed separatelv. The "Stereochemistrv" review contains &onnation about the g0al and scope of the series). Trenn's hook, which begins with a foreword by Glenn T. Seahorg, himself a Nobel Laureate in Chemistry (1951), is a unique blend of the old and the new. Believing that "the speculation surrounding the transmutation of matter seemsquite unrivalled in the entire history of science," Trenn surveys his chosen theme from "the alchemical tradition dating hack over two thousand years2'tothe latest developments in nuclear technology such as the fusion power toroid reactor, which he views as the modern version of the worm of Owohoros-the tail-devouring serpent, a key alchemical symbol of the unity of matter. He pursues this unusual and provocative juxtaposition of the ancient and the modern consistently throughout the book, and he finds interesting parallels between central concepts of the ancient hermetic art and modem discoveries of nuclear chemistry and physics. For example, he sees natural and artificial transmutations as fulfillments of alchemical prophecies with subatomic particles functioning both as prima moterio and as the philosophers' stone. And although modern nuclear "alchemists" have succeeded a t tremendous cost in transmuting other elements, e.g., mercury and bismuth, into gold, Trenn, like Frederick Soddy before him, regards the true "gold" of such transfornations not as the noble metal itself but as the tremendous amount of energy released during sueh changes. In Chapter 1(30 pp.), which is alliteratively titled "Adepts, Awards, and Achievements'' ("adept" being the classical title of alchemists who had attained the secret of transmutation), Trenn prefaces the three publications by the Nobel Laureates with a 7-page "Biographical Introduction." The publications themselves are all the products of teamwork-"Radioactive Change" by Ernest Rutherford and Frederick Soddy (theory of atomic disintegration, 1903); "A New Type of Radioactivity" by Irene Curie and Fdd6ric Joliot (discovery of artificial radioactivity, 1934); and "Concerning the Existence and Behavior of Alkaline Earth Metals Resulting from Neutron Irradiation of Uranium by Otto Hahn and Fritz Strassmann (discovery of nuclear fission, 1939). Rutherford received the Nobel Prize in Chemistry in 1908, Soddy in 1921, Joliot and Joliot-Curie in 1935, and Hahn and Strassmann, together with Lise Meitner, in 1944. Chapters 2 and 3 survey the progress of alchemy "From Antiquity to Paracelsus" (14 pp.) and "From Paracelsus to Late Nineteenth Century" (12 pp.), respectively. Chapter 4, "Transmutation in the Twentieth Century," the longest in the book (40 pp.), is divided into five sections"Natural Transmutation: 18961905;" "Artificial Transmutation: 1906-1919;" "Artificial Radioactivity: 1920-1935;" "Discovery of Fission: 19361940," and "Controlled Transmutation: 1941-1981." Each of these sections is provided with an Introduction and Conclusion which link the events to ancient alchemical concepts. Chapter 5, "Future Expectations" (12 pp.), deals with recent attempts t o put transmutation "on line" to produce energy, "the new gold." Among the topics discussed are fissile and fertile fuel, the thorium cycle, breeder, fusion, and hybrid reactors, plutonium, waste, and conservation. Trenn also

clearly differentiates the reactor made from the bomb mode of transmutation. To meet our increasing need for energy Trenn views contralled transmutation as "the only viable option for the coming generation or two." He thinks that fusion power is the ultimate power source, hut until it can he achieved economically, he favors global use of fission power. The text concludes with a 2-page epilogue, Chapter 6, "Reflections on Transmutation." Since the volume is not intended for the professional historian but far "the chemist, the researcher worker and the nonspecialist," the number of references is minimal (16), hut appendices provide a 3-page chronology, "Some Historical Data on Transmutation," a 3-page "Glossary" (defining technical terms in the text which are marked with asterisks), and a 3-page list of "Suggested Reading." Subject (6 pp.) and name (2 pp.) indices conclude the volume. The few errors are minor misspellings ("corpuscle" on p. 58 and Strassmann on o. 118). This scholarlv but readable hook orovides an excellent intro, duttion to harh alrhrmy aud nuclear rhemistry, while it simullaneuu,ly underwores the generally neglected relationship between the two. George - B. Kauffman California State University. Fresno Fresna. CA 93740 ~~

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Total Synthesis of Natural Products: T h e 'Chiron' Approach Stephen Hanessian, Pergamon Press, Elmsford. NY, 1983. xviii 291 pp. Figures. $20.00 PB and $40.00 HE.

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This hook is a detailed study of the use of carbohydrate derivatives as chiral starting materials for the synthesis of chiral natural products. I t is a highly specialized book, intended for use by professional synthetic organic chemists and advanced graduate students. A "chiron" (contraction of "chiral svnthon"). is e d a i n e d to beanenantiomerirally purp '.synthm." gcnrraliy i h t i n c d inrm an nminuacd, a terpcne,or acarlmhg. dmte. T h r book's title ir rmwwhat misleading, because its thorough coverage is limited to the use of carbohydrates. "The 'Chiron' Approach" hegins with a brief section on strategy, reviewing the types of chiral orecursors and erolainine how to find carhihydrate-typesym;nrtry i n natural p r d u r t s that du not supcriirially rcwmhle carh~,hydmtes.'l'hc rest o f t h r twok rewews over 100 natural product syntheses that exploit the stereochemistry present in earbohydrates. The brief discussions of synthetic strategy are accompanied by retrosynthetic flaw charts and the actual svntheses with , reagents. A brief drscriprion of the nuthor's romputer-assisted synrhrm program cump l e w the htmk. An excrilmr Index r ~ f e r e n c e ~ the names of the natural products synthesized, those used as synthetic precursors, and the types of reactions and reagents used. This book might be criticized for its lack of coverage of noncarbohydrate "chirons" and for its heavy emphasis on the author's own work. On the other hand, Hanessian has covered his own specific area of interest and expertise in an authoritative, current, and

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complete manner. An additional criticism is the lack of claritvin the author's writhe-stvle. . The sentences are long and ccmvoluted, and the Innwage isoften stilted. Although "The 'Chiron' Approach" may force organic chemists to review their carbohydrate chemistry, it is an important piece of reading for those interested in natural product synthesis. I t sets forth the principles that the author and others have used ta synthesize chiral natural products by exploiting the stereochemistry present in other, more common, natural products. Leroy G. Wade, Jr. Colwado State University Fon Collins, CO 80523

Quantum Chemistry, Thlrd EdRion Ira N. Levine, Allyn and Bacon, Inc., Rockleigh, NJ, 1983. x 566 pp. Figs. and tables. 16.5 X 24 cm.

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This is the third edition of a successful introductory graduate text, first published in 1970. The author writes clearly, with refreshing warmth and humor. Mathematical demands are minimal. Mast topics are introduced as dimessions within the bodv of the text. As hefore. the author has manaeed ~~, ~~~, . ~to trmt quantum mechanics with very littie reference to spertnaropy: this is n faruu which may limn ilu urdulnesa in some courses. This edition is about 10%larger than the previous one, due to the inclusion of additional material throughout the hook. There are many new end-of-chapter problems as well. New sections have been written on the particle in a rectangular well, molecular vibration, time-dependent perturbation theory, the Condon-Slater rules, configuration interaction wave functions, and Hartree-Fock methods for molecules. Chapter 9 now includes a brief section on the interaction of electromagnetic radiation with matter, so that students will at least be introduced to electronic transitions. Particularly welcome is the extensive enlargement of Chapter 15, on the structure of molecules. This includes new information on population analysis, free-electron molecular orbitals, and pielectron systems. A new section introduces matrix algebra, but matrix notation is not found elsewhere in the book. Most physics texts now use SI units exclusively, and today's students expect to see electromagnetic equations in MKS form. Some of the equations in this edition have been rewritten to follow this usage, butmany are still shown essentially in electrostatic units. Althoueh new references are cited throuehout "~~ th; book. the hulk of the literaturr mentioned is still from the I96U's. The *ection on computers is somewhat uut of date. Modern students do not need definitions of microcomputer and program; they would benefit more from a discussion of the types of algorithms used in quantum chemical calculations and their relative efficiencies. This textbook has all of the strenahs of its orieinnl edition and is enhanced 6v the in" clu3ion of new topics. I t is not mathematically xophisticntd, it is extremely rendable, and it will continue to be an excellent introductory work for many years to come. Edward Finkel Fernbank Science Center ~~~

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Altanta. GA 30307

Volume 6 2

Number 6

June 1965

A191