AWARDS
ACS 1989 Award Winners Following are vignettes of the Arthur C. Cope Award winner, and nine recipients of Arthur C. Cope Scholar Awards. They will receive their awards at the annual Arthur C. Cope Symposium organized by the ACS Division of Organic Chemistry. The symposium will be held in Miami Beach during the ACS national meeting Sept. 10-15,1989. The Arthur C. Cope Scholar Awards recognize and encourage excellence in organic chemistry. Each award consists of a certificate and a $15,000 unrestricted research grant to be assigned by the recipient to any university or nonprofit institution. The recipients are required to deliver a lecture at the Arthur C. Cope Symposium.
Arthur C. Cope Award WILLIAM S. JOHNSON, JacksonWood Professor of Chemistry emeritus, Stanford University, has been called "one of the fathers of the revolution in synthesis." When he began working with the preparation of steroids, the field of synthesis was in its infancy. His contributions, spanning some 50 years, "have changed the way organic chemists practice their science," says an admiring colleague. Johnson received his M.A. and Ph.D. degrees from Harvard University in 1938 and 1940, respectively. His early years in teaching were spent at the University of Wisconsin, where he became full professor in 1946 and Homer Adkins Professor of Chemistry in 1960. Also in 1960, he was named professor and executive head of the department of chemistry at Stanford University. He attained his present title there in 1975, and became emeritus in 1978. His work breaks into two major periods: t h e Wisconsin p e r i o d , where he employed traditional annulation chemistry to build up the complex structures of steroids; and the more recent Stanford period,
where he evaluated the role of enzymes in mediating reactions versus the intrinsic chemistry of the reacting system. His development of chiral acetals as initiators for polyolefin cyclization has spawned activity in using such a strategy as a broad-based approach for asymmetric synthesis. Many of Johnson's earlier contributions have been recognized with the ACS Award for Creative Work in Synthetic Organic Chemistry in 1958, the Synthetic Organic Chemical Manufacturers Award for Creative Research in Organic Chemistry in 1963, the ACS New York Section's Nichols Medal in 1968, and France's Roussel Prize in 1970. More recently, he was honored with the Roger Adams Award in Organic Chemistry in 1977 and the National Medal of Science in 1987. He has lectured throughout the U.S., in Switzerland, the U.K., the Nether-
lands, France, Australia, Germany, and Japan. An ACS member since 1937, Johnson served as chairman of the Wisconsin Section in 1949 and chairman of the Organic Chemistry Division in 1951. He was a member of the ACS Committee on Professional Training from 1952 to 1956, and served on the executive board of the Journal of Organic Chemistry from 1954 to 1956 and the editorial board of the Journal of the American Chemical Society from 1956 to 1965. He has been active in other organizations as well, serving as secretary of the organic section, International Union of Pure & Applied Chemistry Congress in 1951, and as a member of the National Science Foundation's chemistry advisory panel from 1952 to 1956. In 1970-74, he was a member of the National Institutes of Health medicinal chemistry study section.
Arthur C. Cope Scholar Awards
through the Quantum Chemistry Exchange Program, effective computer programs that can be used by any chemist. His most widely recognized work, the molecular mechanics computer program (MM2), has been updated to handle conjugated and aromatic systems, including heterocycles. Novel conjugated pi systems also have commanded his attention, and beginning in the early 1960s, he applied quantum mechanics to organic chemistry. As computers became more powerful, he put them to use in quantum calculations of molecular properties such as electronic spectra, optical rotatory dispersion, and other properties related to conformation. Allinger received a B.S. degree in chemistry in 1951 from the University of California, Berkeley, and a Ph.D. degree, also in chemistry, in 1954 from the University of California, Los Angeles. He also did postdoctoral work at UCLA, and in
NORMAN L. ALLINGER, Research Professor of Chemistry, University of Georgia, has been a pioneer in the use of computers in organic chemistry. According to a colleague, "It would be difficult to find another recent contribution with an impact on the practice of organic chemistry that approaches that of Allinger's work in molecular mechanics." Molecular mechanics replaces the use of mechanical molecular models and guesswork as a method of estimating the energies of molecules in their various conformations. Molecular shapes and energies are obtained from a force field that references experimental measurements for its parameters. Allinger has been influential in bringing the method to a stage in which calculations give results of chemical accuracy for many kinds of organic molecules. In addition, he has made available,
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Awards 1955-56 was a National Science Foundation postdoctoral fellow at Harvard University. He began his teaching career at Wayne State University in 1956, and was made professor in 1960. In the spring of 1968, Allinger went to the University of Georgia as a visiting professor, and r e t u r n e d in 1969 to accept his present position. A frequent lecturer and prolific writer, the award winner has some 250 research papers in refereed journals. He is the editor of the Journal of Computational Chemistry; coauthor of "Organic Chemistry," "Structures of Organic Molecules," "Conformational Analysis," "An Introduction to General, Organic, and Biological Chemistry," and "Molecular Mechanics"; and coeditor of "Topics in Stereochemistry." SCOTT E. DENMARK, professor of chemistry at the University of Illinois, "is an outstanding young scientist whose research in synthetic organic chemistry has attracted both national and international recognition," says an admiring colleague. His research has focused on the invention and development of novel synthetic reactions as new methods for stereocontrolled carboncarbon bond construction. His approach to synthesis methodology is reactivity oriented rather than structure oriented. This is apparent in all his studies in which each new synthetic reaction embodies an interesting question in the relationship between structure and reactivity of a newly devised species or reactive intermediate. Allied with this interest is an area of investigation that addresses fundamental questions about the structure of reactive intermediates and their influence on the stereochemical course of double bond reactions. In the area of new synthetic reac-. tions, his work has focused primarily on pericyclic processes. He has documented new examples in each of the three classes of pericyclic reactions: the silicon-directed Nazarov cyclization, the carbanionic-Claisen rearrangement, and heterodiene [4+2]-cycloadditions of nitroalkenes. His work on the carbanionic-Claisen rearrangement is an example of the 56
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amalgamation of synthetic and mechanistic objectives in his program. Using both carefully designed models and nuclear magnetic resonance studies, Denmark has probed the factors that control the mechanism and stereochemical course of reactions between allylic organometallic reagents (silanes and stannanes) and aldehydes. These models have allowed the first unambiguous i n s i g h t s into t h e relative disposition of the reacting double bonds. More important, these studies have demonstrated the stereochemical significance of the Lewis acid-aldehyde complex. Denmark did his undergraduate work at Massachusetts Institute of Technology, where he worked with both R. H. Holm and D. S. Kemp. He completed his bachelor's degree in 1975, and matriculated at the Eidgenossische Technische Hochschule, Zurich, where he received a D.Sc.Tech. degree in 1980 under the direction of Albert Eschenmoser. Honors include a National Science Foundation Presidential Young Investigator Award for 1985-90, an Alfred P. Sloan Foundation fellowship for 1985-89, and the 1987 Stuart Phamaceuticals Award in Chemistry. Rowland Pettit Centennial Professor at the University of Texas, Austin, MARYE ANNE FOX has had an extraordinarily productive career since she began her scientific work at Texas, in 1976. She has authored or coauthored more than 100 scientific articles and 10 chapters since that time—a record, points out one colleague, that few, if any, scientists of her generation can equal.
Denmark
Fox's research has been aimed at solving major problems in organic photochemistry and electrochemistry. She and her coworkers have virtually pioneered the interdisciplinary field of organic photoelectrochemistry. One of the unusual aspects of her research program is its breadth. She displays an impressive mastery of problems found in physical, inorganic, and analytical chemistry and applies this ability to tackling problems of organic chemistry. She and her group are equally at home handling, for instance, semiempirical calculations, transient spectroscopy, or organic synthesis. The award winner was one of the first researchers to apply the research techniques of physical organic chemistry to reactions occurring on surfaces and to recognize semiconductor particles as ideal microenvironments for initiating controlled redox chemistry. Her studies of potential organic-based solar energy storage systems have been unique. And, according to a colleague, "The implications of her current mechanistic work in polymers will surely find great importance in the burgeoning area of material science." Fox received a B.S. degree from Notre Dame College in 1969, an M.S. degree from Cleveland State University in 1970, and a Ph.D. from Dartmouth College in 1974. From 1974 to 1976 she was a postdoctoral fellow at the University of Maryland. She joined the faculty at the University of Texas in 1976 as assistant professor and was appointed to her present post last year. She is a member of the editoral advisory boards of The Journal of
Organic Chemistry and ACS Symposium Series and Advances in Chemistry, and is an associate editor of the Journal of the American Chemical Society. In addition, she is a member of the board, Commission on Physical Sciences, Mathematics, and Resources of the National Research Council. According to a colleague, no one has come close to JEREMY R. KNOWLES, Amory Houghton Professor of Chemistry and Biochemistry at Harvard University, "in the elegance in design and execution of experimental work in mechanistic chemistry related to enzymology." Also winner of the 1989 Bader Award in Bioinorganic or Bioorganic Chemistry, Knowles was educated at Magdalen College School, Oxford, and received his master's and doctorate degrees in 1961 from Oxford University. He was a research fellow in 1961-62 at California Institute of Technology, and then returned to Dyson Perrins Laboratory, Oxford. He was a University Lecturer at the University of Oxford from 1966 until 1974, when he came to the U.S. as professor of chemistry at Harvard. He was appointed to his present chair in 1979. Knowles 7 early work at Oxford dealt with the specificity and mechanism of proteases such as a-chymotrypsin and pepsin. His later work on acyl nitrenes as photoactive reagents—first for antibody labeling and then for biological receptors in general—opened the way for hundreds of such studies over the past two decades. His move to Harvard foreshadowed the first of three research ac-
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complishments that changed the way all enzymologists think about biological catalysis. This is the work on the energetics of the glycolytic enzyme triosephosphate isomerase. In a series of ground-breaking papers, Knowles and W. J. Albery showed how to use and analyze substrate and solvent deuterium and tritium isotope effects to define, for the first time, the energetics of a biological catalyst at work. More recently, Knowles and his group tackled the catalytic mechanism of the enzyme ^-lactamase, which is the major molecular cause of clinical penicillin resistance. By applying Fourier-transform infrared spectroscopy, they proved that an acyl enzyme intermediate occurs in the hydrolytic pathway. They then used this knowledge to rationalize how a new generation of naturally occurring and synthetic penicillins act as mechanism-based inactivators of the lactamase. In the past 10 years, Knowles' group has spearheaded many exciting advances: in the study of dozens of enzymes involved in phosphoryl transfer by the development of chiral [ 16 0, 1 7 0 , 1 8 0]-phosphoryl groups; in resolving the stereochemical course of such reactions as that catalyzed by chorismate mutase; and in the ingenious use of isotope effects to evaluate the concertedness of enzymatic processes. JERROLD MEINWALD, Goldwin Smith Professor of Chemistry at Cornell University, is being recognized for his broad-ranging contributions to organic chemistry. Meinwald's studies on insect defense and communication mecha-
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nisms have had great scientific impact and he is probably best known for his research in this area. His pioneering investigations, largely in collaboration with Cornell colleague Thomas Eisner, have revealed that a remarkably wide variety of organic compounds is used in arthropod defense. His research on insect pheromones has also added significantly to the understanding of chemical communication. He has characterized and synthesized the components that constitute the first example of a pulsed, airborne chemical signal. The discovery of temporal modulation, made in collaboration with Eisner and William Conner, has added a new dimension to the understanding of chemical signaling. In his most recent work, he has elucidated the roles played by pyrrolizidine alkaloids in insect defense, communication, and sexual selection. Meinwald's extensive studies of plant/insect interactions have revealed the biological roles of many natural products. He is a leader in the field of chemical ecology, and currently serves as president of the International Society of Chemical Ecology. After a stint in the Navy as an electronics technician, Meinwald received Ph.B. (1947) and B.S. (1948) degrees from the University of Chicago, and M.A. (1950) and Ph.D. (1952) degrees from Harvard University. Except for a year at the University of California, San Diego, Meinwald's entire teaching career has been at Cornell University. He is an elected member of the American Philosophical Society (1987), the American Academy of Arts & Sci-
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Awards hold important positions in both industry and academe. The award winner currently has a group of nine graduate students and an equal number of postdoctoral associates. He is an eloquent speaker who has delivered numerous plenary lectures and conducted seminars worldwide.
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ences (1970), and the National Academy of Sciences (1969). He has been Fogarty Scholar-in-Residence at the National Institutes of Health (198385) and a Guggenheim fellow (1960, 1976). Among the other honors that he has received are the Distinguished Scientist Award, presented by the ACS Kalamazoo Section (1985); the Ernest Guenther Award in the Chemistry of Essential Oils & Related Products (1984); and a 1983 Japan Society for the Promotion of Science fellowship. He was chairman of the ACS Organic Chemistry Division in 1969. LARRY E. OVERMAN, professor of chemistry, University of California, Irvine, has made significant contributions to synthetic organic chemistry, in both methodology and total synthesis. "Overman," says a colleague, "is a major player in utilizing pericyclic reactions for the synthesis of heterocycles." The award winner developed a number of innovative reactions that include the tandem aza-Cope rearrangement-Mannich cyclization, vinylsilane-terminated imminium ion cyclizations, and oxonium ion mediated ene cyclizations. Overman's approach to synthetic methodology portrays an extraordinary level of mechanistic analysis. He has repeatedly shown a talent for providing.new solutions to synthetic transformations and then demonstrated their utility in innovative ways in a variety of total synthesis problems. He achieved worldwide recognition for his efforts with the pumiliotoxin alkaloids. His most recent accomplish58
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ments include the enantioselective total synthesis of streptazolin, the total synthesis of (—)-laurenyne, and his work on furan annulations. "A consistent trademark of his research," comments a colleague, "is a high level of creativity in the design stage [combined with] an ability to successfully execute at the strategic level the difficult total synthesis." Overman received a B.A. degree (1965) from Earlham College, Richmond, Ind., and a Ph.D. degree (1969) from the University of Wisconsin, Madison. After two years as a postdoctoral fellow at Columbia University under Ronald Breslow, Overman came to UC Irvine. He has received numerous awards including Alfred P. Sloan Foundation fellow (1975-77), Camille and Henry Dreyfus teacher-scholar award (1976-81), UC Irvine Distinguished Teaching Award (1981), Alexander von Humboldt senior scientist award (1985-87), and Javits neuroscience investigator award (1985-92). The award winner's professional activities include member of the executive committee of the Division of Organic Chemistry (1985-88), the board of editors of Organic Syntheses (1986-94) a n d Organic Reactions (1984-89), and the editorial advisory board of The Journal of Organic Chemistry (1985-89). He has been a consultant to Allergen Pharmaceuticals, a subsidiary of SmithKline Beckman, since 1983; to SmithKline Beckman since 1986; and to Syntex Research since 1987. From California to New York in the U.S., and in England, France, Switzerland, Mexico, Canada, Japan, and Australia, Overman's former students and postdoctoral associates
For nearly 40 years, ANDREW STREITWIESER JR., professor of chemistry, University of California, Berkeley, has made important experimental and theoretical contributions to organic, physical organic, and organometallic chemistry. Streitwieser was one of the first to prepare optically active compounds with H-D asymmetry and to use these compounds in studying the stereochemistry of various reactions at primary alkyl functional groups. Among other advances, these studies led to a new mechanism for transalkylation of ethylbenzene. In further work with deuterium and isotope effects, the award winner was first to determine an a-deuterium secondary isotope effect in the solvolysis of cyclopentyl1-d tosylate. He correctly interpreted the effect in terms of simple C-H bending motions and pointed out that its magnitude could provide a valuable tool for studying the structures of transition states. Streitwieser published a series of papers on deuterium and tritium exchange reactions in experimental studies of the kinetic acidities of weak acids. In other kinetic studies, particularly with lithium and cesium cyclohexamide in cyclohexamine, he contributed greatly to an understanding of the effects of structure and of ion pairing. Streitwieser's reviews have been a valuable service to organic chemists. His 1956 "Solvolytic Displacement Reactions" came at an opportune time in modern carbonium ion chemistry and is one of the earliest organic works making use of orbital diagrams. His 1961 book, "Molecular Orbital Theory for Organic Chemists," contained a comprehensive review of the literature, served as a textbook, and included a great deal of his own research. Beyond his book, the award winner made numerous contributions to theoret-
ical organic chemistry. He was one of the first to show that d-orbitals on sulfur are chemically unimportant in understanding sulfur-stabilized carbanions. He was one of the pioneers in the use of electron density functions and diagrams in interpreting organic chemistry. More recently he has studied the C-Li bond in methyllithium, and suggests that the bond is more ionic than had been previously thought. Streitwieser has contributed much to organoactinide and lanthanide chemistry. His discovery of uranocene awakened much of the modern effort in this area. Recently his group determined the phenyl rotation barrier in l,l'-diphenyluranocene, confirmed the existence of cerocene, and developed a simple synthesis. The award winner received an A.B. degree (1948) from Columbia College and M.A. (1950) and Ph.D. (1952) degrees from Columbia University. He has over 300 publications, and has trained more than 100 Ph.D.s and postdoctoral associates. He has won numerous awards. "An international leader in synthetic organic chemistry" is how one colleague sizes up the stature of BARRY M. TROST, professor of chemistry at Stanford University. The majority of the award winner's contributions have come from his design of reagents and reactions to change the rules of selectivity of organic reactions. Recognizing the usefulness of small ring fragments to selectively manipulate structures, Trost devised a series of reagents that smoothed the way to incorporating such a structural feature in organic molecules. He has used this concept to take advantage of the timed release of strain energy to create a wide range of molecular architecture, including cyclobutanes, cyclopentanes, lactones, geminally substituted systems, and a variety of acyclic units. Trost has pioneered the use of the organic chemistry of sulfur to control the behavior of organic molecules. His research has led to such synthetic concepts as sulfenylation, dehydrosulfenylation, alkylative carbonyl transposition, alkylative elim-
ination, oxidative secorearrangement, and oxidative decarboxylation. Changing the rules of selectivity for carbon-carbon bond formation emerges from the work of Trost. Transition metal complexes derived from molybdenum, tungsten, nickel, and especially palladium become templates for controlling the behavior of organic substrates with enzymelike precision. The ability to create unstable intermediates on a metal template translates into a cycloaddition strategy to rings of [2n + 3] members that complements the Diels-Alder reaction. Trost's studies of the organic chemistry of silicon have resulted in a three-carbon intercalation that creates a practical approach to musk compounds. And he has been a key researcher in the creation and implementation of the first new polymerization method in years—group transfer polymerization. Trost received a Ph.D. degree from Massachusetts Institute of Technology in 1965 and joined the University of Wisconsin as assistant professor. He was chairman of the department of chemistry from 1980 to 1982, when he was appointed Vilas Research Professor of Chemistry. He came to Stanford in 1987. He has authored several books and has about 350 publications to his credit. Among his many honors are the ACS Award in Pure Chemistry in 1977 and the ACS Award for Creative Work in Synthetic Organic Chemistry in 1981. He was elected to the National Academy of Sciences in 1980 and to the American Academy of Arts & Sciences in 1982. GEORGE M. WHITESIDES, Mallinckrodt Professor of Chemistry and chairman of the d e p a r t m e n t of chemistry at Harvard University, has made many key and original contributions to physical organic chemistry. These include the use of nuclear magnetic resonance (NMR) to study dynamic stereochemical problems, the elucidation of the mechanisms of organometallic reagents and reactions, the nature of heterogeneous reactions, and the use of enzymes in synthesis. In his work with NMR spectroscopy, Whitesides carried out the first
applications of dynamic line-shape analysis to coupled spin systems. He was the first to show experimentally the mechanism of pseudorotation in the analysis of the spectra of pentacovalent complexes. He invented the chiral europium shift reagent, which is now widely used for chiral perturbation in analyzing enantiomeric purity. Among his many firsts in transition metal organometallic chemistry are the activation of carbonhydrogen bonds by homogeneous platinum(O) complexes, synthesis and characterization of a transition metal metallocycle, and demonstration of t h e relevance of metallocycles in catalysis. In addition, he was among the first to develop synthetic uses of organocuprates in organic chemistry. In Whitesides' investigation of heterogeneous reactions, he tackled the complex mechanism of the formation of Grignard reagents using electron microscopy to study the surface and the spinning disk electrode to follow the kinetics. First of its type, this research demonstrated the importance of mass transport close to the interface and discredited the concept of "surface-bound radicals." In other research, he examined the platinum-catalyzed oxidation of alcohols and the heterogeneous catalyzed reductions of homogeneous transition metal alkyls. More recently the award winner has used enzymes as reagents for large-scale syntheses. His most outstanding achievements in this area are the development of methods for cofactor regeneration and the use of multienzyme systems that contain up to 20 enzymes. He has well over 200 publications and his list of honors is a long one, including an Alfred P. Sloan Fellowship in 1968, ACS Award in Pure Chemistry in 1975, Harrison Howe Award in 1979, and the Remsen Award in 1983. Whitesides received an A.B. degree from Harvard in 1960 and a Ph.D. from California Institute of Technology in 1964. He joined the faculty at MIT in 1963 as assistant professor and rose through the ranks to Haslam and Dewey Professor in 1980. In 1982 he came to Harvard to assume his present post. • December 5, 1988 C&EN
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