Robert Burns Woodward
|Died||July 8, 1979 62) (aged|
Cambridge, Massachusetts, U.S.
|Alma mater||MIT (S.B., Ph.D.)|
|Doctoral advisor|| James Flack Norris |
Avery Adrian Morton [ citation needed ]
Robert Burns Woodward (April 10, 1917 – July 8, 1979) was an American organic chemist. He is considered by many to be the preeminent organic chemist of the twentieth century,having made many key contributions to the subject, especially in the synthesis of complex natural products and the determination of their molecular structure. He also worked closely with Roald Hoffmann on theoretical studies of chemical reactions. He was awarded the Nobel Prize in Chemistry in 1965.
Organic chemistry is the chemistry subdiscipline for the scientific study of structure, properties, and reactions of organic compounds and organic materials. Study of structure determines their chemical composition and formula. Study of properties includes physical and chemical properties, and evaluation of chemical reactivity to understand their behavior. The study of organic reactions includes the chemical synthesis of natural products, drugs, and polymers, and study of individual organic molecules in the laboratory and via theoretical study.
Organic synthesis is a special branch of chemical synthesis and is concerned with the intentional construction of organic compounds. Organic molecules are often more complex than inorganic compounds, and their synthesis has developed into one of the most important branches of organic chemistry. There are several main areas of research within the general area of organic synthesis: total synthesis, semisynthesis, and methodology.
Roald Hoffmann is a Polish-American theoretical chemist who won the 1981 Nobel Prize in Chemistry. He has also published plays and poetry. He is the Frank H. T. Rhodes Professor of Humane Letters, Emeritus, at Cornell University, in Ithaca, New York.
Woodward was born in Boston, Massachusetts, to Margaret (née Burns, an immigrant from Scotland, and a descendant of Robert Burns, the poet) and Arthur Chester Woodward, son of Roxbury, Massachusetts apothecary, Harlow Elliot Woodward. When Robert was one year old, his father died in the flu pandemic of 1918.
From a very early age, Woodward was attracted to and engaged in private study of chemistry while he attended a public primary school, and then Quincy High School, [ citation needed ] although it is not clear whether he actually took any of their advice. After a short postdoctoral stint at the University of Illinois, he took a Junior Fellowship at Harvard University from 1937 to 1938, and remained at Harvard in various capacities for the rest of his life. In the 1960s, Woodward was named Donner Professor of Science, a title that freed him from teaching formal courses so that he could devote his entire time to research.in Quincy, Massachusetts. By the time he entered high school, he had already managed to perform most of the experiments in Ludwig Gattermann's then widely used textbook of experimental organic chemistry. In 1928, Woodward contacted the Consul-General of the German consulate in Boston (Baron von Tippelskirch ), and through him, managed to obtain copies of a few original papers published in German journals. Later, in his Cope lecture, he recalled how he had been fascinated when, among these papers, he chanced upon Diels and Alder's original communication about the Diels–Alder reaction. Throughout his career, Woodward was to repeatedly and powerfully use and investigate this reaction, both in theoretical and experimental ways. In 1933, he entered the Massachusetts Institute of Technology (MIT), but neglected his formal studies badly enough to be excluded at the end of the 1934 fall term. MIT readmitted him in the 1935 fall term, and by 1936 he had received the Bachelor of Science degree. Only one year later, MIT awarded him the doctorate, when his classmates were still graduating with their bachelor's degrees. Woodward's doctoral work involved investigations related to the synthesis of the female sex hormone estrone. MIT required that graduate students have research advisors. Woodward's advisors were James Flack Norris and Avery Adrian Morton,
Chemistry is the scientific discipline involved with elements and compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they undergo during a reaction with other substances.
Quincy High School (QHS) is a public secondary school located on Coddington Street in Quincy, Massachusetts. It doubles as one of two high schools in the city of Quincy and as the vocational center. Quincy's mascot is known as the 'Presidents' and their school colors are Blue & White.
Quincy is the largest city in Norfolk County, Massachusetts, United States. It is part of Metropolitan Boston and one of Boston's immediate southern suburbs. Its population in 2014 was 93,397, making it the eighth-largest city in the state. Known as the "City of Presidents," Quincy is the birthplace of two U.S. presidents—John Adams and his son John Quincy Adams—as well as John Hancock, a President of the Continental Congress and the first signer of the Declaration of Independence.
The first major contribution of Woodward's career in the early 1940s was a series of papers describing the application of ultraviolet spectroscopy in the elucidation of the structure of natural products. Woodward collected together a large amount of empirical data, and then devised a series of rules later called the Woodward's rules, which could be applied to finding out the structures of new natural substances, as well as non-natural synthesized molecules. The expedient use of newly developed instrumental techniques was a characteristic Woodward exemplified throughout his career, and it marked a radical change from the extremely tedious and long chemical methods of structural elucidation that had been used until then.
Ultraviolet (UV) designates a band of the electromagnetic spectrum with wavelength from 10 nm to 400 nm, shorter than that of visible light but longer than X-rays. UV radiation is present in sunlight, and contributes about 10% of the total light output of the Sun. It is also produced by electric arcs and specialized lights, such as mercury-vapor lamps, tanning lamps, and black lights. Although long-wavelength ultraviolet is not considered an ionizing radiation because its photons lack the energy to ionize atoms, it can cause chemical reactions and causes many substances to glow or fluoresce. Consequently, the chemical and biological effects of UV are greater than simple heating effects, and many practical applications of UV radiation derive from its interactions with organic molecules.
Spectroscopy is the study of the interaction between matter and electromagnetic radiation. Historically, spectroscopy originated through the study of visible light dispersed according to its wavelength, by a prism. Later the concept was expanded greatly to include any interaction with radiative energy as a function of its wavelength or frequency, predominantly in the electromagnetic spectrum, though matter waves and acoustic waves can also be considered forms of radiative energy; recently, with tremendous difficulty, even gravitational waves have been associated with a spectral signature in the context of LIGO and laser interferometry. Spectroscopic data are often represented by an emission spectrum, a plot of the response of interest as a function of wavelength or frequency.
Woodward's rules, named after Robert Burns Woodward and also known as Woodward–Fieser rules are several sets of empirically derived rules which attempt to predict the wavelength of the absorption maximum (λmax) in an ultraviolet–visible spectrum of a given compound. Inputs used in the calculation are the type of chromophores present, the substituents on the chromophores, and shifts due to the solvent. Examples are conjugated carbonyl compounds, conjugated dienes, and polyenes.
In 1944, with his post doctoral researcher, William von Eggers Doering, Woodward reported the synthesis of the alkaloid quinine, used to treat malaria. Although the synthesis was publicized as a breakthrough in procuring the hard to get medicinal compound from Japanese occupied southeast Asia, in reality it was too long and tedious to adopt on a practical scale. Nevertheless, it was a landmark for chemical synthesis. Woodward's particular insight in this synthesis was to realise that the German chemist Paul Rabe had converted a precursor of quinine called quinotoxine to quinine in 1905. Hence, a synthesis of quinotoxine (which Woodward actually synthesized) would establish a route to synthesizing quinine. When Woodward accomplished this feat, organic synthesis was still largely a matter of trial and error, and nobody thought that such complex structures could actually be constructed. Woodward showed that organic synthesis could be made into a rational science, and that synthesis could be aided by well-established principles of reactivity and structure. This synthesis was the first one in a series of exceedingly complicated and elegant syntheses that he would undertake.
William von Eggers Doering was a Professor Emeritus at Harvard University and the former Chair of its Chemistry Department. Prior to joining the Faculty at Harvard, he was a member of the Chemistry Faculties of Columbia University (1942–1952) and Yale (1952–1968).
Alkaloids are a class of naturally occurring organic compounds that mostly contain basic nitrogen atoms. This group also includes some related compounds with neutral and even weakly acidic properties. Some synthetic compounds of similar structure may also be termed alkaloids. In addition to carbon, hydrogen and nitrogen, alkaloids may also contain oxygen, sulfur and, more rarely, other elements such as chlorine, bromine, and phosphorus.
Quinine is a medication used to treat malaria and babesiosis. This includes the treatment of malaria due to Plasmodium falciparum that is resistant to chloroquine when artesunate is not available. While used for restless legs syndrome, it is not recommended for this purpose due to the risk of side effects. It can be taken by mouth or used intravenously. Malaria resistance to quinine occurs in certain areas of the world. Quinine is also the ingredient in tonic water that gives it its bitter taste.
Culminating in the 1930s, the British chemists Christopher Ingold and Robert Robinson among others had investigated the mechanisms of organic reactions, and had come up with empirical rules which could predict reactivity of organic molecules. Woodward was perhaps the first synthetic organic chemist who used these ideas as a predictive framework in synthesis. Woodward's style was the inspiration for the work of hundreds of successive synthetic chemists who synthesized medicinally important and structurally complex natural products.
During the late 1940s, Woodward synthesized many complex natural products including quinine, cholesterol, cortisone, strychnine, lysergic acid, reserpine, chlorophyll, cephalosporin, and colchicine.With these, Woodward opened up a new era of synthesis, sometimes called the 'Woodwardian era' in which he showed that natural products could be synthesized by careful applications of the principles of physical organic chemistry, and by meticulous planning.
Many of Woodward's syntheses were described as spectacular by his colleagues and before he did them, it was thought by some that it would be impossible to create these substances in the lab. Woodward's syntheses were also described as having an element of art in them, and since then, synthetic chemists have always looked for elegance as well as utility in synthesis. His work also involved the exhaustive use of the then newly developed techniques of infrared spectroscopy and later, nuclear magnetic resonance spectroscopy. Another important feature of Woodward's syntheses was their attention to stereochemistry or the particular configuration of molecules in three-dimensional space. Most natural products of medicinal importance are effective, for example as drugs, only when they possess a specific stereochemistry. This creates the demand for 'stereoselective synthesis', producing a compound with a defined stereochemistry. While today a typical synthetic route routinely involves such a procedure, Woodward was a pioneer in showing how, with exhaustive and rational planning, one could conduct reactions that were stereoselective. Many of his syntheses involved forcing a molecule into a certain configuration by installing rigid structural elements in it, another tactic that has become standard today. In this regard, especially his syntheses of reserpine and strychnine were landmarks.
During World War II, Woodward was an advisor to the War Production Board on the penicillin project. Although often given credit for proposing the beta-lactam structure of penicillin, it was actually first proposed by chemists at Merck and Edward Abraham at Oxford and then investigated by other groups, as well (e.g., Shell). Woodward at first endorsed an incorrect tricyclic (thiazolidine fused, amino bridged oxazinone) structure put forth by the penicillin group at Peoria. Subsequently, he put his imprimatur on the beta-lactam structure, all of this in opposition to the thiazolidine – oxazolone structure proposed by Robert Robinson, the then leading organic chemist of his generation. Ultimately, the beta-lactam structure was shown to be correct by Dorothy Hodgkin using X-ray crystallography in 1945.
Woodward also applied the technique of infrared spectroscopy and chemical degradation to determine the structures of complicated molecules. Notable among these structure determinations were santonic acid, strychnine, magnamycin and terramycin. About terramycin, Woodward's colleague and Nobel Laureate Derek Barton said:
In each one of these cases, Woodward again showed how rational facts and chemical principles, combined with chemical intuition, could be used to achieve the task.
In the early 1950s, Woodward, along with the British chemist Geoffrey Wilkinson, then at Harvard, postulated a novel structure for ferrocene, a compound consisting of a combination of an organic molecule with iron.This marked the beginning of the field of transition metal organometallic chemistry which grew into an industrially very significant field. Wilkinson won the Nobel Prize for this work in 1973, along with Ernst Otto Fischer. Some historians think that Woodward should have shared this prize along with Wilkinson. Remarkably, Woodward himself thought so, and voiced his thoughts in a letter sent to the Nobel Committee.
Woodward won the Nobel Prize in 1965 for his synthesis of complex organic molecules. He had been nominated a total of 111 times from 1946 to 1965.In his Nobel lecture, he described the total synthesis of the antibiotic cephalosporin, and claimed that he had pushed the synthesis schedule so that it would be completed around the time of the Nobel ceremony.
In the early 1960s, Woodward began work on what was the most complex natural product synthesized to date—vitamin B12. In a remarkable collaboration with his colleague Albert Eschenmoser in Zurich, a team of almost one hundred students and postdoctoral workers worked for many years on the synthesis of this molecule. The work was finally published in 1973, and it marked a landmark in the history of organic chemistry. The synthesis included almost a hundred steps, and involved the characteristic rigorous planning and analyses that had always characterised Woodward's work. This work, more than any other, convinced organic chemists that the synthesis of any complex substance was possible, given enough time and planning (see also palytoxin, synthesized by the research group of Yoshito Kishi, one of Woodward's postdoctoral students). As of 2016, no other total synthesis of Vitamin B12 has been published.
That same year, based on observations that Woodward had made during the B12 synthesis, he and Roald Hoffmann devised rules (now called the Woodward–Hoffmann rules) for elucidating the stereochemistry of the products of organic reactions.Woodward formulated his ideas (which were based on the symmetry properties of molecular orbitals) based on his experiences as a synthetic organic chemist; he asked Hoffman to perform theoretical calculations to verify these ideas, which were done using Hoffmann's Extended Hückel method. The predictions of these rules, called the "Woodward–Hoffmann rules" were verified by many experiments. Hoffmann shared the 1981 Nobel Prize for this work along with Kenichi Fukui, a Japanese chemist who had done similar work using a different approach; Woodward had died in 1979 and Nobel Prizes are not awarded posthumously.
While at Harvard, Woodward took on the directorship of the Woodward Research Institute, based at Basel, Switzerland, in 1963.He also became a trustee of his alma mater, MIT, from 1966 to 1971, and of the Weizmann Institute of Science in Israel.
Woodward died in Cambridge, Massachusetts from a heart attack in his sleep. At the time, he was working on the synthesis of an antibiotic, erythromycin. A student of his said about him:
During his lifetime Woodward authored or coauthored almost 200 publications, of which 85 are full papers, the remainder comprising preliminary communications, the text of lectures, and reviews. The pace of his scientific activity soon outstripped his capacity to publish all experimental details, and much of the work in which he participated was not published until a few years after his death. Woodward trained more than two hundred Ph.D. students and postdoctoral workers, many of whom later went on to distinguished careers.
Some of his best-known students include Robert M. Williams (Colorado State), Harry Wasserman (Yale), Yoshito Kishi (Harvard), Stuart Schreiber (Harvard), William R. Roush (Scripps-Florida), Steven A. Benner (UF), Christopher S. Foote (UCLA), Kendall Houk (UCLA), porphyrin chemist Kevin M. Smith (LSU), Thomas R. Hoye (University of Minnesota), Ronald Breslow (Columbia University) and David Dolphin (UBC).
Woodward had an encyclopaedic knowledge of chemistry, and an extraordinary memory for detail.Probably the quality that most set him apart from his peers was his remarkable ability to tie together disparate threads of knowledge from the chemical literature and bring them to bear on a chemical problem.
For his work, Woodward received many awards, honors and honorary doctorates, including election to the National Academy of Sciences in 1953, and membership in academies around the world. He was also a consultant to many companies such as Polaroid, Pfizer, and Merck. Other awards include:
Woodward also received over twenty honorary degrees,including honorary doctorates from the following universities:
In 1938 he married Irja Pullman; they had two daughters: Siiri Anna (b. 1939) and Jean Kirsten (b. 1944). In 1946, he married Eudoxia Muller, an artist and technician whom he met at the Polaroid Corp. This marriage, which lasted until 1972, produced a daughter, and a son: Crystal Elisabeth (b. 1947), and Eric Richard Arthur (b. 1953).
His lectures frequently lasted for three or four hours. [ citation needed ] He detested exercise, could get along with only a few hours of sleep every night, was a heavy smoker, and enjoyed Scotch whisky and martinis.His longest known lecture defined the unit of time known as the "Woodward", after which his other lectures were deemed to be so many "milli-Woodwards" long. In many of these, he eschewed the use of slides and drew structures by using multicolored chalk. Typically, to begin a lecture, Woodward would arrive and lay out two large white handkerchiefs on the countertop. Upon one would be four or five colors of chalk (new pieces), neatly sorted by color, in a long row. Upon the other handkerchief would be placed an equally impressive row of cigarettes. The previous cigarette would be used to light the next one. His Thursday seminars at Harvard often lasted well into the night. He had a fixation with blue, and many of his suits, his car, and even his parking space were coloured in blue. In one of his laboratories, his students hung a large black and white photograph of the master from the ceiling, complete with a large blue "tie" appended. There it hung for some years (early 1970s), until scorched in a minor laboratory fire.
Chemical synthesis is a purposeful execution of chemical reactions to obtain a product, or several products. This happens by physical and chemical manipulations usually involving one or more reactions. In modern laboratory usage, this tends to imply that the process is reproducible, reliable, and established to work in multiple laboratories.
Elias James "E.J." Corey is an American organic chemist. In 1990, he won the Nobel Prize in Chemistry "for his development of the theory and methodology of organic synthesis", specifically retrosynthetic analysis. Regarded by many as one of the greatest living chemists, he has developed numerous synthetic reagents, methodologies and total syntheses and has advanced the science of organic synthesis considerably.
Vladimir Prelog ForMemRS was a Croatian-Swiss organic chemist who received the 1975 Nobel Prize in chemistry for his research into the stereochemistry of organic molecules and reactions. Prelog was born and grew up in Sarajevo. He lived and worked in Prague, Zagreb and Zürich during his lifetime.
Donald James Cram was an American chemist who shared the 1987 Nobel Prize in Chemistry with Jean-Marie Lehn and Charles J. Pedersen "for their development and use of molecules with structure-specific interactions of high selectivity." They were the founders of the field of host–guest chemistry.
Kenichi Fukui was a Japanese chemist, known as the first Asian scientist to receive a chemistry Nobel Prize.
Total synthesis is the complete chemical synthesis of a complex molecule, often a natural product, from simple, commercially available precursors. It usually refers to a process not involving the aid of biological processes, which distinguishes it from semisynthesis. The target molecules can be natural products, medicinally important active ingredients, or organic compounds of theoretical interest. Often the aim is to discover new route of synthesis for a target molecule for which there already exist known routes. Sometimes no route exists and the chemist wishes to find a viable route for the first time. One important purpose of total synthesis is the discovery of new chemical reactions and new chemical reagents.
Jean-Marie Lehn is a French chemist. He received the Nobel Prize in Chemistry together with Donald Cram and Charles Pedersen in 1987 for his synthesis of cryptands. Lehn was an early innovator in the field of supramolecular chemistry, i.e., the chemistry of host–guest molecular assemblies created by intermolecular interactions, and continues to innovate in this field. As of January 2006, his group has published 790 peer-reviewed articles in chemistry literature.
Robert Howard Grubbs, ForMemRS, is an American chemist and the Victor and Elizabeth Atkins Professor of Chemistry at the California Institute of Technology in Southern California. He was a co-recipient of the 2005 Nobel Prize in Chemistry for his work on olefin metathesis. He is a co-founder of Materia, a University spin-off startup to produce catalysts.
Kyriacos Costa Nicolaou is a Cypriot-American chemist known for his research in the area of natural products total synthesis. He is currently Harry C. and Olga K. Wiess Professor of Chemistry at Rice University, having previously held academic positions at The Scripps Research Institute/UC San Diego and the University of Pennsylvania.
The Willard Gibbs Award, presented by the Chicago Section of the American Chemical Society, was established in 1910 by William A. Converse (1862–1940), a former Chairman and Secretary of the Chicago Section of the society and named for Professor Josiah Willard Gibbs (1839–1903) of Yale University. Gibbs, whose formulation of the Phase Rule founded a new science, is considered by many to be the only American-born scientist whose discoveries are as fundamental in nature as those of Newton and Galileo.
The timeline of chemistry lists important works, discoveries, ideas, inventions, and experiments that significantly changed humanity's understanding of the modern science known as chemistry, defined as the scientific study of the composition of matter and of its interactions. The history of chemistry in its modern form arguably began with the Irish scientist Robert Boyle, though its roots can be traced back to the earliest recorded history.
The total synthesis of quinine, a naturally-occurring antimalarial drug, was developed over a 150-year period. The development of synthetic quinine is considered a milestone in organic chemistry although it has never been produced industrially as a substitute for natural occurring quinine. The subject has also been attended with some controversy: Gilbert Stork published the first stereoselective total synthesis of quinine in 2001, meanwhile shedding doubt on the earlier claim by Robert Burns Woodward and William Doering in 1944, claiming that the final steps required to convert their last synthetic intermediate, quinotoxine, into quinine would not have worked had Woodward and Doering attempted to perform the experiment. A 2001 editorial published in Chemical & Engineering News sided with Stork, but the controversy was eventually laid to rest once and for all when Williams and coworkers successfully repeated Woodward's proposed conversion of quinotoxine to quinine in 2007.
Carl Shipp "Speed" Marvel has been considered "one of the world's outstanding organic chemists." Throughout his career, almost no area of polymer chemistry escaped his interest. He made important contributions to U.S. synthetic rubber program during World War II, and later worked at developing polybenzimidazoles, temperature-resistant polymers that are used in the aerospace industry, in fire-fighting equipment, and as a replacement for asbestos. He received numerous awards, including the 1956 Priestley Medal and the 1986 National Medal of Science, presented by President Ronald Reagan.
Albert Eschenmoser (born 5 August 1925) is a Swiss organic chemist best known for his work on the synthesis of complex heterocyclic natural compounds, most notably vitamin B12. In addition to his significant contributions to the field of organic synthesis, Eschenmoser pioneered work in the Origins of Life (OoL) field with work on the synthetic pathways of artificial nucleic acids. Before retiring in 2009, Eschenmoser held tenured teaching positions at the ETH Zurich and The Skaggs Institute for Chemical Biology at The Scripps Research Institute in La Jolla, California as well as visiting professorships at the University of Chicago, Cambridge University, and Harvard.
Ian Fleming is an English organic chemist, and an emeritus professor of the University of Cambridge, and an emeritus fellow of Pembroke College, Cambridge. He was the first to determine the full structure of chlorophyll and was involved in the development of the synthesis of cyanocobalamin by Robert Burns Woodward. He has made major contributions to the use of organosilicon compounds for stereospecific syntheses; reactions which have found application in the synthesis of natural compounds. He is also a prolific author, and has written a number of textbooks, encyclopedia chapters and influential review articles.
Phil S. Baran is a Professor in the Department of Chemistry at the Scripps Research Institute and Member of the Skaggs Institute for Chemical Biology. He received his B.S. in chemistry from New York University in 1997 and his Ph.D. from The Scripps Research Institute in 2001, under the supervision of K.C. Nicolaou. He did his postdoctoral fellowship in the laboratory of Nobel Laureate E. J. Corey at Harvard University.
Jeffrey I. Seeman is a historian of science, chemist, and Visiting Senior Research Scholar in the Department of Chemistry at the University of Richmond in Richmond, Virginia. He is the editor of 20+ volumes in the series Profiles, pathways and dreams : autobiographies of eminent chemists. In addition to writing extensively as both a scientist and historian, he has produced short films for historical and educational use.
Prof. Robert Burns Woodward, the Harvard chemist who synthesized quinine, cortisone and rauwolfia, has now achieved one of the greatest triumphs in chemistry -- the total synthesis of chlorophyll, the green pigment that captures the energy of sunlight for the creation of the food for all things living. ...
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