Robert Burns Woodward
Robert Burns Woodward | |
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Born | Boston,Massachusetts,U.S. | April 10, 1917
Died | July 8, 1979 | (aged 62)
Alma mater | Massachusetts Institute of Technology(BS,PhD) |
Known for | |
Awards |
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Scientific career | |
Fields | Organic chemistry |
Institutions | Harvard University |
Thesis | A Synthetic Attack on the Oestrone Problem(1937) |
Doctoral advisor | James Flack Norris Avery Adrian Morton[2] |
Doctoral students |
Robert Burns WoodwardForMemRSHonFRSE(April 10, 1917 – July 8, 1979) was an Americanorganic chemist.He is considered by many to be the preeminent synthetic organic chemist of the twentieth century,[3]having made many key contributions to the subject, especially inthe synthesis of complex natural productsand the determination of theirmolecular structure.He worked closely withRoald Hoffmannon theoretical studies ofchemical reactions.He was awarded theNobel Prize in Chemistryin 1965.
Early life and education
[edit]Woodward was born inBoston, Massachusetts,on April 10, 1917. He was the son of Margaret Burns (an immigrant from Scotland who claimed to be a descendant of the poet,Robert Burns) and her husband, Arthur Chester Woodward, himself the son ofRoxburyapothecary, Harlow Elliot Woodward.
His father was one of the many victims of the1918 influenza pandemic.
From a very early age, Woodward was attracted to and engaged in private study ofchemistrywhile he attended a public primary school, and thenQuincy High School,[4]inQuincy, Massachusetts.By the time he entered high school, he had already managed to perform most of the experiments inLudwig 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[5]), 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 theDiels–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 theMassachusetts 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 theBachelor of Sciencedegree. Only one year later, MIT awarded him thedoctorate,when his classmates were still graduating with their bachelor's degrees.[6]Woodward's doctoral work involved investigations related to the synthesis of the female sex hormoneestrone.[7]MIT required that graduate students have research advisors. Woodward's advisors wereJames Flack Norrisand Avery Adrian Morton,[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 atHarvard Universityfrom 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.
Research and career
[edit]Early work
[edit]The first major contribution of Woodward's career in the early 1940s was a series of papers describing the application ofultravioletspectroscopyin 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 theWoodward'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.
In 1944, with his post doctoral researcher,William von Eggers Doering,Woodward reported the synthesis of thealkaloidquinine,used to treatmalaria.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 realize 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.
Later work and its impact
[edit]![](https://upload.wikimedia.org/wikipedia/commons/thumb/b/bd/Robert_Burns_Woodward_in_1965.jpg/220px-Robert_Burns_Woodward_in_1965.jpg)
Culminating in the 1930s, the British chemistsChristopher IngoldandRobert Robinsonamong 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.
Organic syntheses and Nobel Prize
[edit]This sectionneeds additional citations forverification.(June 2024) |
During the late 1940s, Woodward synthesized many complex natural products includingquinine,cholesterol,cortisone,strychnine,lysergic acid,reserpine,chlorophyll,cephalosporin,andcolchicine.[8]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 ofphysical 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 ofinfrared spectroscopyand later,nuclear magnetic resonancespectroscopy.Another important feature of Woodward's syntheses was their attention tostereochemistryor 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 theWar Production Boardon the penicillin project. Although often given credit for proposing thebeta-lactamstructure ofpenicillin,it was actually first proposed by chemists atMerckandEdward Abrahamat Oxford and then investigated by other groups, as well (e.g., Shell). Woodward at first endorsed an incorrect tricyclic (thiazolidinefused, amino bridged oxazinone) structure put forth by the penicillin group at Peoria. Subsequently, he put hisimprimaturon the beta-lactam structure, all of this in opposition to thethiazolidine–oxazolonestructure proposed byRobert Robinson,the then leading organic chemist of his generation. Ultimately, the beta-lactam structure was shown to be correct byDorothy HodgkinusingX-ray crystallographyin 1945.
Woodward also applied the technique ofinfrared spectroscopyand chemical degradation to determine the structures of complicated molecules. Notable among these structure determinations weresantonic acid,strychnine,magnamycinandterramycin.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 chemistGeoffrey Wilkinson,then at Harvard, postulated a novel structure forferrocene,a compound consisting of a combination of an organic molecule with iron.[9]This marked the beginning of the field oftransition metalorganometallic chemistrywhich grew into an industrially very significant field.[10]Wilkinson won the Nobel Prize for this work in 1973, along withErnst Otto Fischer.[11]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.[12]
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.[13]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.
B12synthesis and Woodward–Hoffmann rules
[edit]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 colleagueAlbert Eschenmoserin 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 alsopalytoxin,synthesized by the research group ofYoshito Kishi,one of Woodward's postdoctoral students). As of 2019, no othertotal synthesis of Vitamin B12has been published.
That same year, based on observations that Woodward had made during the B12synthesis, he andRoald Hoffmanndevised rules (now called theWoodward–Hoffmann rules) for elucidating thestereochemistryof the products oforganicreactions.[14]Woodward formulated his ideas (which were based on thesymmetryproperties ofmolecular 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'sExtended 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 withKenichi 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.
Woodward Institute
[edit]While at Harvard, Woodward took on the directorship of the Woodward Research Institute,based atBasel,Switzerland, in 1963.[15]He also became a trustee of his alma mater,MIT,from 1966 to 1971, and of theWeizmann Institute of Sciencein Israel.[citation needed]
Death
[edit]Woodward died inCambridge, Massachusetts,from aheart attackin his sleep. At the time, he was working on the synthesis of anantibiotic,erythromycin.A student of his said about him:[citation needed]
- I owe a lot to R. B. Woodward. He showed me that one could attack difficult problems without a clear idea of their outcome, but with confidence that intelligence and effort would solve them. He showed me the beauty of modern organic chemistry, and the relevance to the field of detailed careful reasoning. He showed me that one does not need to specialize. Woodward made great contributions to the strategy of synthesis, to the deduction of difficult structures, to the invention of new chemistry, and to theoretical aspects as well. He taught his students by example the satisfaction that comes from total immersion in our science. I treasure the memory of my association with this remarkable chemist.
Publications
[edit]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 includeRobert M. Williams(Colorado State), Harry Wasserman (Yale),Yoshito Kishi(Harvard),Stuart Schreiber(Harvard),William R. Roush(Scripps-Florida),Steven A. Benner(UF),James D. Wuest(Montreal),Christopher S. Foote(UCLA),Kendall Houk(UCLA), porphyrin chemist Kevin M. Smith (LSU), Thomas R. Hoye (University of Minnesota),Ronald Breslow(Columbia University) andDavid Dolphin(UBC).
Woodward had an encyclopedic knowledge of chemistry, and an extraordinary memory for detail.[16]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.[16]
Honors and awards
[edit]For his work, Woodward received many awards, honors and honorary doctorates, including election to theAmerican Academy of Arts and Sciencesin 1948,[17]theNational Academy of Sciencesin 1953,[18]theAmerican Philosophical Societyin 1962,[19]and membership in academies around the world. He was also a consultant to many companies such as Polaroid,Pfizer,andMerck.Other awards include:
- John Scott Medal,from theFranklin Instituteand City ofPhiladelphia,1945
- Leo Hendrik Baekeland Award,from the North Jersey Section of theAmerican Chemical Society,1955[20]
- Elected aForeign Member of the Royal Society (ForMemRS) in 1956[1]
- Davy Medal,from theRoyal Societyin 1959
- Roger Adams Medal, from the American Chemical Society in 1961[citation needed]
- Pius XI Gold Medal, from the Pontifical Academy of Sciences in 1969[citation needed]
- National Medal of Sciencefrom the United States in 1964 ( "For an imaginative new approach to the synthesis of complex organic molecules and, especially, for his brilliant syntheses of strychnine, reserphine, lysergic acid, and chlorophyll.")
- Nobel Prize in Chemistryin 1965
- Willard Gibbs Awardfrom theChicagoSection of the American Chemical Society in 1967[21]
- Lavoisier Medalfrom theSociété chimique de Francein 1968
- TheOrder of the Rising Sun,Second Class from the Emperor of Japan in 1970
- Hanbury Memorial Medal from The Pharmaceutical Society of Great Britain in 1970[citation needed]
- Pierre Bruylants Medal from theUniversity of Louvainin 1970[citation needed]
- AMA Scientific Achievement Awardin 1971
- Cope Awardfrom the American Chemical Society, shared withRoald Hoffmannin 1973
- Copley Medalfrom the Royal Society, London in 1978
Honorary degrees
[edit]Woodward also received over twentyhonorary degrees,[22]including honorary doctorates from the following universities:
- Wesleyan Universityin 1945;
- Harvard Universityin 1957;
- University of Cambridgein 1964;[citation needed]
- Brandeis Universityin 1965;
- Technion Israel Institute of TechnologyinHaifain 1966;
- University of Western Ontarioin Canada in 1968;
- University of Louvainin Belgium, 1970.
Personal life
[edit]Family
[edit]In 1938, he married Irja Pullman; they had two daughters: Siiri Anna (b. 1939) and Jean Kirsten (b. 1944). In 1946, he marriedEudoxia Muller,an artist and technician whom he met atthe Polaroid Corp.This marriage, which lasted until 1972, produced a daughter, and a son: Crystal Elisabeth (b. 1947), and Eric Richard Arthur (b. 1953).[6]
Idiosyncrasies
[edit]His lectures frequently lasted for three or four hours.[5]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.[23]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.[5]
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.[citation needed]He detested exercise, could get along with only a few hours of sleep every night, was aheavy smoker,and enjoyed Scotch whisky and martinis.[1][24]
References
[edit]- ^abcTodd, L.; Cornforth, J.; T., A. R.; C., J. W. (1981). "Robert Burns Woodward. 10 April 1917-8 July 1979".Biographical Memoirs of Fellows of the Royal Society.27:628–695.doi:10.1098/rsbm.1981.0025.ISSN0080-4606.S2CID71742454.
- ^Woodward, Robert Burns (1937).A synthetic attack on the oestrone problem(Thesis). MIT.hdl:1721.1/12465.
- ^Elkan Blout (2001). "Robert Burns Woodward".Biographical Memoirs of the National Academy of Sciences.80. | url =http:// nasonline.org/publications/biographical-memoirs/memoir-pdfs/woodward-robert-b.pdf
- ^Putnam, Robert C. (2001). Benfey, Otto Theodor; Turnbull Morris, Peter John (eds.).Reminiscences From Junior High School.Chemical Heritage Foundation. p. 12.ISBN9780941901253.
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ignored (help) - ^abcRemembering organic chemistry legend Robert Burns Woodward Famed chemist would have been 100 this yearBy Bethany Halford C&EN Volume 95 Issue 15 | pp. 28–34 Issue Date: April 10, 2017link.
- ^abThe Nobel Prize in Chemistry 1965 – Robert B. Woodward BiographyNobelprize.org
- ^A synthetic attack on the oestrone problem PhD dissertation
- ^"Chlorophyll".The New York Times.July 3, 1960.RetrievedOctober 13,2012.
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....
- ^Wilkinson, G.;Rosenblum, M.; Whiting, M. C.;Woodward, R. B.(1952). "The Structure of IronBis-Cyclopentadienyl ".J. Am. Chem. Soc.74(8): 2125–2126.doi:10.1021/ja01128a527.
- ^Federman Neto, A.; Pelegrino, A. C.; Darin, V. A. (2004). "Ferrocene: 50 Years of Transition Metal Organometallic Chemistry — From Organic and Inorganic to Supramolecular Chemistry".ChemInform.35(43).doi:10.1002/chin.200443242.
- ^"The Nobel Prize in Chemistry 1973".nobelprize.org.RetrievedSeptember 12,2010.
- ^Werner, H. (2008).Landmarks in Organo-Transition Metal Chemistry: A Personal View.Springer Science. pp. 161–163.ISBN978-0-387-09847-0.
- ^"Nomination Archive".April 2020.
- ^Hoffmann, R.;Woodward, R. B.(1970). "Orbital Symmetry Control of Chemical Reactions".Science.167(3919) (published February 6, 1970): 825–831.Bibcode:1970Sci...167..825H.doi:10.1126/science.167.3919.825.PMID17742608.S2CID12243669.
- ^Craig, G. Wayne (2011). "The Woodward Research Institute, Robert Burns Woodward (1917–1979) and Chemistry behind the Glass Door".Helvetica Chimica Acta.94(6): 923–946.doi:10.1002/hlca.201100077.
- ^abRoberts, J. (1990).The Right Place at the Right Time.American Chemical Society.ISBN978-0-8412-1766-9.
- ^"Robert Burns Woodward".American Academy of Arts & Sciences.RetrievedNovember 14,2022.
- ^"Robert Woodward".nasonline.org.RetrievedNovember 14,2022.
- ^"APS Member History".search.amphilsoc.org.RetrievedNovember 14,2022.
- ^AwardsNorth Jersey Section American Chemical Society – see section Current & Past Recipients of the Leo Hendrik Baekeland Award
- ^American Chemical Society – Chicago Section
- ^Blout, Elkan."Robert Burns Woodward 1917–1979: A Biographical Memoir"(PDF).National Academy of Sciences.The National Academy Press.RetrievedJanuary 15,2017.
- ^(in French)Introduction à la chimie quantiquePhilippe Hiberty and Nguyên Trong Anh, Editions Ecole Polytechnique Renaud-Bray (2008) p.115ISBN2730214852
- ^Robert Burns WoodwardArchivedApril 27, 2012, at theWayback Machine.
Bibliography
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- Robert Burns Woodward: Architect and Artist in the World of Molecules; Otto Theodor Benfey, Peter J. T. Morris, Chemical Heritage Foundation, April 2001.
- Robert Burns Woodward and the Art of Organic Synthesis: To Accompany an Exhibit by the Beckman Center for the History of Chemistry (Publication / Beckman Center for the History of Chemistry); Mary E. Bowden; Chemical Heritage Foundation, March 1992
- Woodward R. B.; Sondheimer F.; Taub D. (1951). "The Total Synthesis of Cortisone".Journal of the American Chemical Society.73(8): 4057.doi:10.1021/ja01152a551.
- George B. Kauffman (2004). "Organic Synthesizer par excellence – On the 25th Anniversary of His Death".Chem. Educator.9:1–5.
- Robert Burns Woodwardon Nobelprize.org
- Video podcast of Robert Burns Woodward talking about cephalosporin
- Robert Burns Woodward: Three Score Years and Then?David Dolphin,Aldrichimica Acta,1977,10(1), 3–9.
- Robert Burns Woodward Patents
External links
[edit]![](https://upload.wikimedia.org/wikipedia/commons/thumb/f/fa/Wikiquote-logo.svg/34px-Wikiquote-logo.svg.png)
- Notes from Robert Burns Woodward's Seminarstaken by Robert E. Kohler inScience History Institute Digital Collections
- Robert Burns Woodwardon Nobelprize.org including the Nobel Lecture, December 11, 1965Recent Advances in the Chemistry of Natural Products
- 1917 births
- 1979 deaths
- 20th-century American chemists
- 20th-century American educators
- American Nobel laureates
- American science writers
- Foreign Members of the Royal Society
- Harvard University faculty
- Massachusetts Institute of Technology alumni
- Wesleyan University people
- Nobel laureates in Chemistry
- National Medal of Science laureates
- American organic chemists
- Stereochemists
- People from Belmont, Massachusetts
- Recipients of the Copley Medal
- 20th-century American writers
- Time Person of the Year
- Members of the American Philosophical Society
- Quincy High School (Massachusetts) alumni