Robert Burns Woodward

Robert Burns Woodward

Robert Burns Woodward
Born (1917-04-10)April 10, 1917
Boston, Massachusetts, U.S.
Died July 8, 1979(1979-07-08) (aged 62)
Cambridge, Massachusetts, U.S.
Citizenship United States
Fields Organic chemistry
Institutions Harvard University
Alma mater MIT
Doctoral students Harry Wasserman · Christopher Foote
Ken Houk · Ronald Breslow
Stuart Schreiber · William R. Roush
Known for Landmark organic syntheses
Molecular structure determination
Woodward–Hoffmann rules
Notable awards Davy Medal (1959)
National Medal of Science (1964)
Nobel Prize in Chemistry (1965)
Willard Gibbs Award (1967)
Copley Medal (1978)

Robert Burns Woodward (April 10, 1917 – July 8, 1979) was an American 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.

Contents

  • Early life and education 1
  • Early work 2
  • Later work and its impact 3
    • Organic syntheses and Nobel Prize 3.1
    • B12 synthesis and Woodward–Hoffmann rules 3.2
  • Woodward Institute and later life 4
  • Family 5
  • Publications 6
  • Idiosyncrasies 7
  • Honors/Awards 8
  • Honorary degrees 9
  • See also 10
  • References 11
  • Sources 12
  • External links 13

Early life and education

Woodward was born in Boston, Massachusetts, to Margaret (née Burns, an immigrant from Scotland) 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 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.[3] Woodward's doctoral work involved investigations related to the synthesis of the female sex hormone estrone.[4] MIT required that graduate students have research advisors. Woodward's advisors were James Flack Norris and Avery Adrian Morton,[5] 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.

Early work

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.

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.

Later work and its impact

Woodward talked about Chlorophyll in 1965

Culminating in the 1930s, the British chemists

  • Chemistry Tree: Robert B. Woodward Details
  • Robert Burns Woodward
  • 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 Woefully incomplete list; see Discussion pages.

External links

  1. Elkan Blout (2001). "Robert Burns Woodward". Biographical Memoirs of the National Academy of Sciences 80. 
  2. Robert Burns Woodward: Architect and Artist in the World of Molecules; Otto Theodor Benfey, Peter J. T. Morris, Chemical Heritage Foundation, April 2001.
  3. 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
  4.  
  5. Woodward R. B., Sondheimer F., Taub D. (1951). "The Total Synthesis of Cortisone". Journal of the American Chemical Society 73 (8): 4057–4057.  
  6. George B. Kauffman (2004). "Organic Synthesizer par excellence – On the 25th Anniversary of His Death". Chem. Educator 9: 1–5. 

Sources

  1. ^ Blout, Elkan (2001). "Biographical Memoirs".  
  2. ^ Putnam, Robert C. (2001). Benfey, Otto Theodor; Turnbull Morris, Peter John, eds. Reminiscences From Junior High School. Robert Burns Woodward: Architect and Artist in the World of Molecules (Chemical Heritage Foundation). p. 12. 
  3. ^ a b The Nobel Prize in Chemistry 1965 - Robert B. Woodward Biography Nobelprize.org
  4. ^ A synthetic attack on the oestrone problem PhD dissertation
  5. ^ Robert B. Woodward Chemistry Tree profile
  6. ^ "Chlorophyll".  
  7. ^  
  8. ^ 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).  
  9. ^ "The Nobel Prize in Chemistry 1973".  
  10. ^ Werner, H. (2008). Landmarks in Organo-Transition Metal Chemistry: A Personal View. Springer Science. pp. 161–163.  
  11. ^  
  12. ^ Hickenboth, Charles R.; Moore, Jeffrey S.; White, Scott R.; Sottos, Nancy R.; Baudry, Jerome; Wilson, Scott R. (2007). "Biasing reaction pathways with mechanical force". Nature 446 (7134): 423–7.   (See also the corresponding "News and Views" in the same issue of Nature)
  13. ^ 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.  
  14. ^ a b Roberts, J. (1990). The Right Place at the Right Time.  
  15. ^ Robert Burns Woodward
  16. ^  
  17. ^ American Chemical Society - Chicago Section

References

See also

Woodward also received over twenty honorary degrees, including honorary doctorates from the following universities:

Honorary degrees

Other awards include:

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.

Honors/Awards

His lectures frequently lasted for three or four hours. 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. 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.[15][16]

Idiosyncrasies

Woodward had an encyclopaedic knowledge of chemistry, and an extraordinary memory for detail.[14] 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.[14]

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, Ronald Breslow (Columbia University) and David Dolphin (UBC).

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.

Publications

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).[3]

Family

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.

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:

While at Harvard, Woodward took on the directorship of the Woodward Research Institute, based at Basel, Switzerland, in 1963.[13] He also became a trustee of his alma mater, MIT, from 1966 to 1971, and of the Weizmann Institute of Science in Israel.

Woodward Institute and later life

Note that a recent paper in the journal Nature describes how mechanical stress can be used to effect novel ring-opening reactions violating the orbital symmetry based predictions of the Woodward–Hoffmann rules.[12] Since heat is randomly directed mechanical energy, it seems unfair to consider it the same as the directed mechanical energy employed in the Nature article. Thus, the Nature reaction is neither a (1) heat-activated ring-opening nor (2) light-activated ring-opening (The two possibilities considered by the Woodward–Hoffmann rules). Heat and light-activated reactions are probably more fundamental to a synthetic chemist, since extra steps of tethering a bulky group to the molecule (as was done in the Nature article) and possibly de-tethering the bulky group, is not required.

That same year, based on observations that Woodward had made during the B12 synthesis, he and 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.

In the early 1960s, Woodward began work on what was the most complex natural product synthesized to date- palytoxin, synthesized by the research group of Yoshito Kishi, one of Woodward's postdoctoral students). As of 2006, no other total synthesis of Vitamin B12 has been published.

B12 synthesis and Woodward–Hoffmann rules

Woodward won the Nobel Prize in 1965 for his synthesis of complex organic molecules. 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.

[10] 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.[9].Ernst Otto Fischer Wilkinson won the Nobel Prize for this work in 1973, along with [8] In the early 1950s, Woodward, along with the British chemist

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.

The most brilliant analysis ever done on a structural puzzle was surely the solution (1953) of the terramycin problem. It was a problem of great industrial importance, and hence many able chemists had performed an enormous amount of work trying to determine the structure. There seemed to be too much data to resolve the problem, because a significant number of observations, although experimentally correct, were very misleading. Woodward took a large piece of cardboard, wrote on it all the facts and, by thought alone, deduced the correct structure for terramycin. Nobody else could have done that at the time.

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:

During World War II, Woodward was an advisor to the Dorothy Hodgkin using X-ray crystallography in 1945.

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 the late 1940s, Woodward synthesized many complex natural products including physical organic chemistry, and by meticulous planning.

Organic syntheses and Nobel Prize