Elias James Corey

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EJ Corey (2007)

Elias James Corey (born July 12, 1928 in Methuen , Massachusetts ) is an American chemist and Nobel Prize winner . He is a professor emeritus at Harvard University . His studies over five decades cover almost all areas of organic chemistry and have had a decisive impact on biochemistry and modern medical science.

His work ranges from the basic logic of chemical synthesis to the development of useful reagents such as pyridinium chlorochromate or 1,3-dithianes as a protective group for carbonyl compounds to the invention of numerous synthetic methods. Corey's inventions include organometallic chemistry , catalytic asymmetric reactions , mechanistic insights into bond-forming processes and led to the first use of computers to design synthetic pathways. The synthesis of complex bioactive compounds such as that of several prostaglandins in the 1960s are still considered a milestone in natural product synthesis .

Corey has received over 70 scientific awards. In 1990 he received the Nobel Prize in Chemistry for the development of the theory and methodology of the synthesis of organic compounds , in particular for his establishment of retrosynthesis . EJ Corey has published over 1000 scientific papers and is one of the most cited authors in chemistry. His scientific school produced numerous industrial chemists as well as later professors and Nobel Prize winners such as Ryoji Noyori and Bengt Ingemar Samuelsson .

Life

Childhood and youth

EJ Corey was born in Methuen, a community about 50 kilometers north of Boston , in 1928 as the son of Lebanese Christians under the name William Corey. At the age of 18 months he lost his father and his mother changed his first name to his father's name, Elias. His mother put her household together with his aunt's in order to survive the depression years economically with her four children, two sons and two daughters. His uncle took the place of the father.

View across the Charles River to MIT's domed structure and neighboring buildings

From the age of twelve he attended the Catholic Saint Laurence O'Toole Elementary School in Lawrence and then the Lawrence Public High School. In 1945, at the age of 16, he began studying at the Massachusetts Institute of Technology . Originally interested in mathematics , he soon decided to study chemistry, as he was fascinated by organic chemistry and its relevance to human health. His academic teachers included Arthur C. Cope , John C. Sheehan, and John D. Roberts , among others .

Professor at the University of Illinois

In 1948 he completed his studies with a bachelor's degree . He initially stayed at MIT, where he wrote his dissertation on the synthesis of penicillins ( The synthesis of N, N - diacylamino acids and analogs of penicillin ) in the group of John C. Sheehan and received his doctorate in 1951. Also in 1951 he began his first teaching position as an instructor at the University of Illinois, Urbana-Champaign under Roger Adams and Carl S. Marvel .

Since his interests ranged from theoretical to biochemistry , he researched and taught a wide range of chemistry. In the first three years he researched the field of molecular orbital theory and its importance for the stereochemistry of reactions. As early as 1954, now an assistant professor, he began studying the structure and synthesis of natural products . When he was 27, he got a position as Professor of Organic Chemistry at the University of Illinois. He expanded his research area to include enantioselective synthesis , complex chemistry and the chemistry of enzymes .

Professor at Harvard

Harvard University Science Center

In 1957, Corey received a Guggenheim Fellowship . He spent his research stay with Robert B. Woodward and visited Switzerland, London and Lund in Europe . The first considerations on the rational synthesis of natural products also date from this period. During a stay at Sune Bergström 's first acquaintance with the chemistry of prostaglandins , which led to the first total synthesis of this group of substances in the 1960s.

In 1959, Corey accepted an appointment at the renowned Harvard University . Two years later, in September 1961, he married Claire Higham, with whom he has three children. In 1968, Corey was appointed to the University's Sheldon Emory Chair. At the time, Harvard's chemistry faculty was made up of Paul D. Bartlett , Konrad Bloch , Louis F. Fieser , George Bogdan Kistiakowsky , Eugene G. Rochow , Frank H. Westheimer , Edgar Bright Wilson and Robert B. Woodward.

Pupils

During his time at Harvard, numerous well-known chemists were his doctoral or post-doctoral students.

As PhD students (selection):

As postdocs (selection)

Nobel Prize

At Harvard, EJ Corey conducted research in various areas such as the total synthesis of complex natural products, new synthesis methods, molecular catalysts and theoretical organic chemistry, retrosynthesis and reaction mechanisms . In 1990 his career was crowned with the award of the Nobel Prize in Chemistry .

The 1998 suicide of a Corey student who blamed Corey and abusive research oversight for his suicide in his suicide note caused a stir . The allegations led to temporary changes such as the establishment of an advisory committee. At the time of being awarded the Priestley Medal in 2004, Corey claimed that he gave Robert B. Woodward the crucial pointers in discovering the Woodward-Hoffmann rules . Roald Hoffmann publicly rejected this.

From the beginning of his academic career in New Jersey through 2010, Corey had approximately 700 members on his research group. With over 1100 publications, he received the Cycle of Excellence High Impact Contributor Award in 2007 and was considered the chemist with the highest influence in the Hirsch Index .

Research work

Retrosynthesis and polarity reversal, computer-aided synthesis analysis

Retrosynthetic analysis using the example of prostaglandin F 2α

Corey was introduced to the synthesis of complex molecules early in his career. In the 1950s, it was common practice to plan the synthesis of complex molecules using a trial and error methodology, starting from commercially available or previously described molecules. Molecules such as morphine and cholesterol were considered to be difficult to synthesize.

To enable the efficient production of highly complex molecules , Corey developed what is known as retrosynthesis. This is a technique for planning organic synthesis. A target molecule is broken down into simpler precursor structures, so-called synthons , without making any assumptions about the possible starting materials . Depending on the complexity of the molecule, the precursor materials are further broken down using the same method until simple or commercially available structures are achieved.

The goal of retrosynthesis is structural simplification. A total synthesis can have more than one possible synthetic route. The retrosynthesis enables the examination of different synthetic routes and compares them in a logical way. An electronic database can be used to check at every stage of the analysis whether a precursor component has already been described in the literature. In this case, no further investigation of this connection is necessary.

With Dieter Seebach he developed the concept of polarity reversal .

Synthesis reactions and reagents

In addition, he found numerous other synthetic reactions , such as the Corey-Bakshi-Shibata reduction , the Corey-Fuchs reaction , the Corey-Kim oxidation , the Corey-Winter elimination , the Corey-House-Posner-Whitesides reaction , the Johnson-Corey-Chaykovsky reaction , the Corey-Seebach reaction , the Corey-Schmidt oxidation , the Corey-Gilman-Ganem oxidation and the Corey-Suggs oxidation . The research is based on fundamental theoretical models of stereochemistry , which are developed with the help of computer simulations . This theoretically sound approach to synthesis that he developed was seen by observers as a revolution for chemistry in the 20th century. He also developed the oxidizing agent pyridinium chlorochromate with which, for example, alcohols can be oxidized to aldehydes.

PCC mechanism.png

From 1965, Corey researched the use of 1,3-dithianes as a protective group for carbonyl compounds and developed the concept of polarity reversal in collaboration with Dieter Seebach . The formation of the dithianes, also known as the Corey-Seebach reaction , occurs through the direct reaction of 1,3-propanethiol with carbonyl compounds, such as. B. 1 .

Corey-Seebach reaction

The resulting 1,3-dithianes 2 can be deprotonated by alkyllithium compounds such as n- butyllithium to form an anion 3 . By subsequent reaction with electrophiles and subsequent removal of the protecting group by mercury compounds such as mercury (II) chloride of mercury (II) oxide succeed the linking carbon atoms of the same polarity, thus it forms 5 .

Total syntheses

In the group of Corey many natural substances have been synthesized, including longifolene , ginkgolides , lactacystin , Miroestrol , ecteinascidin 743 and salinosporamideA . In 1978, Corey synthesized gibberellic acid , an important plant hormone with a complex structure. The synthesis of (+) - ginkgolide A, an active ingredient found in the ginkgo tree and used in Chinese folk medicine to treat circulatory disorders in the elderly and in asthma , is a challenge for synthetic chemistry due to its complicated structure. Sales of this natural product alone are estimated at $ 500 million annually.

Corey also synthesized medically important products from what he called the eicosanoid family, such as prostaglandins and leukotrienes. These compounds are involved in the regulatory functions for many physiological processes such as reproduction , blood clotting and pathological processes in the immune system. The importance of this group of substances was underscored by the award of the 1982 Nobel Prize in Physiology or Medicine to Sune Bergström, Bengt Samuelsson and Sir John Robert Vane for the discovery of prostaglandins and related, biologically active substances.

Structure of prostaglandin F 2α

Corey's group synthesized over 250 highly complex organic molecules, including eicosanoids such as prostaglandins and leukotrienes . The prostaglandins are a family of lipids that were discovered in human semen in 1935 by Ulf von Euler and at the same time by MW Goldblatt . Prostaglandins are fatty acid derivatives with 20 carbon atoms and are obtained biochemically from essential fatty acids . They have a variety of pharmacological effects. Prostaglandins act as smooth muscle stimulants and inhibit lipolysis , platelet aggregation and the formation of gastric juice .

In a series of classic publications in 1968 and 1969, Corey described several elegant synthetic methods which are the basis for most of the synthetic work in prostaglandin chemistry. The synthesis of prostaglandin F 2α is a challenge for chemical synthesis because of the presence of cis and trans olefins as well as five asymmetric carbon atoms . Corey retrosynthetic analysis initially began with the separation of the two carbon chains in synthons, which were achieved by means of a Wittig reaction and a Horner-Wadsworth-Emmons reaction can be converted back to the target product. The Wittig reaction produces the cis olefin, while the Horner-Wadsworth-Emmons reaction produces the trans olefin. The reduction of the keto group on the phosphonate by means of zinc borohydride was not stereoselective and still gave the 1: 1 mixture of diastereomers . This synthesis was later achieved using the CBS catalysts that Corey helped develop in a high excess of diastereomers. An iodolactonization leads to an allyl alcohol and another intermediate product, from which a simple Diels-Alder adduct is formed by means of regioselective Baeyer-Villiger oxidation .

Basic structure of the ginkgolide

Corey synthesized Ginkgolide B , a naturally occurring ingredient in the ginkgo tree that has been used in traditional Chinese medicine for the treatment of asthma and circulatory problems for 5,000 years .

Oseltamivir

Structural formula of oseltamivir

In 2006, Corey published a synthesis of oseltamivir (which is sold by Roche under the brand name Tamiflu ® ), which did not start from shikimic acid , but, in contrast to Masakatsu Shibasaki's group, did not take patent protection to make a synthesis possible for everyone.

honors and awards

EJ Corey has received many honors and awards. He was elected to the American Academy of Arts and Sciences in 1960 and to the National Academy of Sciences in 1966 . He received the Ernest Guenther Award in 1968 and the Dickson Prize in Science in 1973 as well as the Linus Pauling Award , the Tetrahedron Prize in 1983 , the Robert Robinson Award in 1988 , the Franklin Medal in 1978, the Paul Karrer Medal in 1982, the Wolf 1986 Chemistry Prize and the National Medal of Science . In 1989 he was awarded the Japan Prize . After winning the Nobel Prize in Chemistry in 1990, he received the Roger Adams Award in 1993 and the Priestley Medal in 2004 . Corey received 19 honorary doctorates from various universities, including Oxford University and Cambridge University . In 2013, the EJ Corey Institute of Biomedical Research (CIBR) opened in Jiangyin . In 2014 he received the Sir Derek H. Barton Gold Medal .

Fonts

Monographs

  • The Logic of Chemical Synthesis. John Wiley & Sons, 1995, ISBN 0-471-11594-0 .
  • with Barbara Czakó and László Kürti: Molecules and Medicine. John Wiley & Sons Publisher, 2007, ISBN 978-0-470-22749-7 .
  • with László Kürti: Enantioselective Chemical Synthesis. Academic Press, 2013, ISBN 978-0-615-39515-9 .

Articles (selection)

  • with Dieter Enders : Synthesis of polyfunctional molecules via metalated dimethylhydrazones. In: Chemical Reports. 111, 1978, pp. 1362-1383, doi: 10.1002 / cber.19781110414 .
  • Elias James Corey: The Logic of Chemical Synthesis: Multistep Synthesis of Complex Carbogenic Molecules (Nobel Lecture). In: Angewandte Chemie International Edition in English. 30, 1991, pp. 455-465, doi: 10.1002 / anie.199104553
  • with Teck Peng Loh, Thomas D. Roper, Mihai D. Azimioara and Mark C. Noe: The origin of greater than 200: 1 enantioselectivity in a catalytic Diels-Alder reaction as revealed by physical and chemical studies. In: Journal of the American Chemical Society. 114, 1992, pp. 8290-8292, doi: 10.1021 / ja00047a050 .
  • with Gregory A. Reichard: Total synthesis of lactacystin. In: Journal of the American Chemical Society. 114, 1992, pp. 10677-10678, doi: 10.1021 / ja00052a096 .
  • with Laurence I. Wu: Enantioselective total synthesis of miroestrol. In: Journal of the American Chemical Society. 115, 1993, pp. 9327-9328, doi: 10.1021 / ja00073a074 .
  • with Mark C. Noe: Rigid and highly enantioselective catalyst for the dihydroxylation of olefins using osmium tetraoxide clarifies the origin of enantiospecificity. In: Journal of the American Chemical Society. 115, 1993, pp. 12579-12580, doi: 10.1021 / ja00079a045 .
  • with SPT Matsuda and B. Bartel: Molecular cloning, characterization, and overexpression of ERG7, the Saccharomyces cerevisiae gene encoding lanosterol synthase. In: Proceedings of the National Academy of Sciences . Volume 91, 1994, p. 2211.

literature

Web links

Commons : EJ Corey  - collection of images, videos and audio files

Individual evidence

  1. ↑ a b c d e f g h i The Nobel Prize in Chemistry 1990: Elias James Corey - Biographical. Retrieved December 15, 2013 .
  2. ↑ biographical data, publications and Academic pedigree of Elias James Corey at academictree.org, accessed on 28 January 2018th
  3. ^ Elias J. Corey, Niels H. Andersen, Robert M. Carlson, Joachim. Paust, Edwin. Vedejs, Isidorus. Vlattas, Rudolph EK Winter: Total synthesis of prostaglandins. Synthesis of the pure dl-E1, -F ( 1α ), -F ( 1β ), -A1, and -B1 hormones. In: Journal of the American Chemical Society. 90, 1968, pp. 3245-3247, doi: 10.1021 / ja01014a053 .
  4. ↑ Elias J. Corey, Isidoros. Vlattas, Niels H. Andersen, Kenn. Harding: A new total synthesis of prostaglandins of the E1 and F1 series including 11-epiprostaglandins. In: Journal of the American Chemical Society. 90, 1968, pp. 3247-3248, doi: 10.1021 / ja01014a054 .
  5. ^ The Nobel Prize in Chemistry 1990 - Elias James Corey. Retrieved December 19, 2013 .
  6. ^ Lethal Chemistry at Harvard, at nytimes.com. Retrieved December 19, 2013 .
  7. ^ Roald Hoffmann: A Claim on the Development of the Frontier Orbital Explanation of Electrocyclic Reactions. In: Angewandte Chemie International Edition. 43, 2004, pp. 6586-6590, doi: 10.1002 / anie.200461440 .
  8. ^ Members of the Corey Group since 1950. Retrieved December 14, 2013 .
  9. ↑ Hirsch index ranks top chemists - April 23, 2007. Retrieved December 19, 2013 .
  10. ↑ List of publications by EJ Corey, at Harvard.edu. Retrieved December 20, 2013 .
  11. ^ A b E. J. Corey: The Logic of Chemical Synthesis: Multistep Synthesis of Complex Carbogenic Molecules (Nobel Lecture). In: Angewandte Chemie International Edition in English. 30, 1991, pp. 455-465, doi: 10.1002 / anie.199104553 .
  12. ^ EJ Corey, Xue-Min Cheng: The Logic of Chemical Synthesis. John Wiley & Sons Publisher, ISBN 0-471-11594-0 .
  13. ^ Dieter Seebach: Methods of reactivity reversal. In: Angewandte Chemie. 91, 1979, pp. 259-278, doi: 10.1002 / anie.19790910404 .
  14. ↑ EJ Corey, D. Seebach: Synthesis of 1, n-Dicarbonyl Derivates Using Carbanions from 1,3-Dithianes. In: Angewandte Chemie International Edition in English. 4, 1965, p. 1077, doi : 10.1002 / anie.196510771 .
  15. ↑ Bengt-Thomas Gröbel, Dieter Seebach: Umpolung of the reactivity of carbonyl compounds through sulfur-containing reagents. In: Synthesis , 1977.6 (1977): pp. 357-402.
  16. ^ EJ Corey, Masaji Ohno, Paul A. Vatakencherry, Rajat B. Mitra: Total Synthesis of d, l-Longifolene. In: Journal of the American Chemical Society. 83, 1961, pp. 1251-1253, doi: 10.1021 / ja01466a056 .
  17. ^ EJ Corey, Masaji. Ohno, Rajat B. Mitra, Paul A. Vatakencherry: Total Synthesis of Longifolene. In: Journal of the American Chemical Society. 86, 1964, pp. 478-485, doi: 10.1021 / ja01057a039 .
  18. ↑ EJ Corey, Arun K. Ghosh: Total synthesis of ginkgolide a. In: Tetrahedron Letters. 29, 1988, pp. 3205-3206, doi : 10.1016 / 0040-4039 (88) 85122-0 .
  19. ↑ a b E. J. Corey, Myung Chol. Kang, Manoj C. Desai, Arun K. Ghosh, Ioannis N. Houpis: Total synthesis of (. + -.) - ginkgolide B. In: Journal of the American Chemical Society. 110, 1988, pp. 649-651, doi: 10.1021 / ja00210a083 .
  20. ↑ EJ Corey, Gregory A. Reichard: Total synthesis of lactacystin. In: Journal of the American Chemical Society. 114, 1992, pp. 10677-10678, doi: 10.1021 / ja00052a096 .
  21. ↑ EJ Corey, Laurence I. Wu: Enantioselective total synthesis of miroestrol. In: Journal of the American Chemical Society. 115, 1993, pp. 9327-9328, doi: 10.1021 / ja00073a074 .
  22. ^ EJ Corey, David Y. Gin, Robert S. Kania: Enantioselective Total Synthesis of Ecteinascidin 743. In: Journal of the American Chemical Society. 118, 1996, pp. 9202-9203, doi: 10.1021 / ja962480t .
  23. ↑ WHO Collaborating Center for Drug Statistics: Trabectedin classification. Retrieved December 26, 2013 .
  24. ↑ Leleti Rajender Reddy, P. Saravanan, EJ Corey: A Simple Stereocontrolled Synthesis of Salinosporamide A. In: Journal of the American Chemical Society. 126, 2004, pp. 6230-6231, doi: 10.1021 / ja048613p .
  25. ↑ Press release for the Nobel Prize ceremony. In: Nobelprize.org. Retrieved January 2, 2014 .
  26. ^ The Nobel Prize in Physiology or Medicine 1982 - Sune K. Bergström, Bengt I. Samuelsson, John R. Vane. Retrieved January 2, 2014 .
  27. ^ EJ Corey: Impossible Dreams. In: The Journal of Organic Chemistry. 69, 2004, pp. 2917-2919, doi: 10.1021 / jo049925d .
  28. ↑ US Euler: About the specific blood pressure lowering substance of the human prostate and seminal vesicle secretion. In: Clinical weekly. 14, 1935, pp. 1182-1183, doi: 10.1007 / BF01778029 .
  29. ^ MW Goldblatt: Properties of human seminal plasma. In: The Journal of Physiology . 84.2 (1935), pp. 208-218.
  30. ^ Sune Bergström, Lars A. Carlson, James R. Weeks: The prostaglandins: a family of biologically active lipids. In: Pharmacological Reviews 20.1 (1968), pp. 1-48.
  31. ^ EJ Corey, Isidorus. Vlattas, Niels H. Andersen, Kenn. Harding: A new total synthesis of prostaglandins of the E1 and F1 series including 11-epiprostaglandins. In: Journal of the American Chemical Society. 90, 1968, pp. 3247-3248, doi: 10.1021 / ja01014a054 .
  32. ↑ EJ Corey, Ned M. Weinshenker, Thomas K. Schaaf, Willy Huber: Stereo-controlled synthesis of dl-prostaglandins F2.alpha. and E2. In: Journal of the American Chemical Society. 91, 1969, pp. 5675-5677, doi: 10.1021 / ja01048a062 .
  33. ↑ EJ Corey, Raman K. Bakshi, Saizo Shibata, Chung Pin Chen, Vinod K. Singh: A stable and easily prepared catalyst for the enantioselective reduction of ketones. Applications to multistep syntheses. In: Journal of the American Chemical Society. 109, 1987, pp. 7925-7926, doi: 10.1021 / ja00259a075 .
  34. ↑ A Short Enantioselective Pathway for the Synthesis of the Anti-Influenza Neuramidase Inhibitor Oseltamivir from 1,3-Butadiene and Acrylic Acid Ying-Yeung Yeung, Sungwoo Hong, and EJ Corey J. Am. Chem. Soc. ; 2006 ; 128 (19) pp 6310-6311; (Communication) doi : 10.1021 / ja0616433
  35. ^ Research groups in the US and Japan develop routes that avoid shikimic acid Chemical & Engineering News 2006 Volume 84, No. 18 p. 5
  36. ^ Priestley Medal goes to EJ Corey, at Pubs.acs.org. Retrieved December 14, 2013 .
  37. ^ EJ Corey, Sheldon Emory Professor Emeritus, Corey's homepage at Harvard University. Retrieved December 14, 2013 .
personal data
SURNAME Corey, Elias James
ALTERNATIVE NAMES Corey, EJ
BRIEF DESCRIPTION American chemist
DATE OF BIRTH July 12, 1928
PLACE OF BIRTH Methuen , Massachusetts