Richard Fred Heck

Richard Fred Heck (born August 15, 1931)[1] is an American chemist noted for the discovery and development of the Heck reaction, which uses the metal palladium to catalyze organic chemical reactions that couple aryl halides with alkenes.

Heck was awarded the Nobel Prize in Chemistry on October 6, 2010, sharing this honor and monetary prize with the Japanese chemists Ei-ichi Negishi and Akira Suzuki, for their work in palladium-catalyzed coupling reactions in organic synthesis.[2]

Life and career

Born in Massachusetts in 1931, Heck earned both his bachelor's degree (1952) and his doctor of philosophy degree (1954) at the University of California, Los Angeles (UCLA), working under the supervision of Dr. Saul Winstein. After two periods of postdoctoral research at the ETH in Zurich, Switzerland, and then back at UCLA, Heck took a position with the Hercules Corporation in Wilmington, Delaware, in 1957. His remarkably productive research work at the Hercules Corp. led to his being hired by the University of Delaware's Department of Chemistry and Biochemistry in 1971. Heck was a professor of chemistry at the University of Delaware until his retirement in the year 1989.

The development of the Heck reaction (sometimes called the "Mizoroki-Heck" Reactions) began with Heck's investigations of the coupling of arylmercury compounds with olefins using palladium as a catalyst during the late 1960s.[3] This work was published in a series of seven consecutive articles in the Journal of the American Chemical Society (JACS) for which Heck was the sole author.[4][5][6][7][8][9]

During the early 1970s Mizoroki[10] and Heck [11] independently reported the use of the less toxic aryl halides as the coupling partner in the reaction. During his career, Heck continued to improve the transformation, developing it into a powerful synthetic method for organic synthesis.

The importance of this reaction grew slowly on the organic synthesis community. In 1982, Heck was able to write an Organic Reactions chapter that covered all the known instances in just 45 pages.[12] By 2002, applications had grown to the extent that the Organic Reactions chapter published that year, limited to intramolecular Heck reactions, covered 377 pages.[13] Today, the Heck reaction stands as one of the widely used methods for the creation of carbon-carbon bonds in the synthesis of organic chemicals. This reaction has been subject to numerous scientific review articles, including a recently published monograph dedicated to this subject.[14]

Palladium-catalyzed coupling reactions
See also: palladium-catalyzed coupling reactions

Heck's work set the stage for a variety of other palladium-catalyzed coupling reactions, including those of aryl halides with derivatives of boronic acid (the Suzuki-Miyaura coupling), organotin reagents (the Stille coupling), organomagnesium compounds (the Kumada-Corriu coupling), silanes (the Hiyama coupling), and organozincs (the Negishi coupling), as well as with alcohols and organic amines. These palladium-catalyzed coupling reactions are now widely practiced in organic synthesis, including in the chemical engineering production of certain organic compounds in factories.

Of the several reactions developed by Heck, the greatest societal impact has been from the palladium-catalyzed coupling of an alkyne with an aryl halide. This is the reaction that was used to couple fluorescent dyes to DNA bases, allowing the automation of DNA sequencing and the examination of the human genome. In Sonogashira's original report of what is now known as the Sonogashira coupling, his group modified an alkyne coupling procedure previously reported by Heck, by adding a copper(I) salt.[15]

Heck's contributions are not limited to the activation of halides by the oxidative addition of palladium. Heck was the first to fully characterize a π-allyl metal complex,[16] and the first to elucidate the mechanism of alkene hydroformylation.[17] Hydroformylation is currently used to produce about 15 billion pounds of alcohols and aldehydes each year.

Retirement and honors

Heck retired from the University of Delaware in 1989, where he remains Willis F. Harrington Professor Emeritus in the Department of Chemistry and Biochemistry. Its annual lectureship was named in his honor in 2004. In 2005, he was awarded the Wallace H. Carothers Award, which recognizes creative applications of chemistry that have had substantial commercial impact. He was awarded the 2006 Herbert C. Brown Award for Creative Research in Synthetic Methods.[18] On 6 October 2010, the Swedish Royal Academy of Sciences awarded Heck the Nobel Prize in Chemistry. He shared the 2010 Nobel Prize with Ei-ichi Negishi and Akira Suzuki "for palladium-catalyzed cross couplings in organic synthesis".[19]

Richard Heck now resides and intends to retire in the Philippines.[20]

References

1. ^ Finucane, Martin (October 6, 2010). "Nobel Prize winner is Springfield native". Boston Globe. http://www.boston.com/news/local/breaking_news/2010/10/nobel_prize_win.html.
2. ^ Press release 6 October 2010. Royal Swedish Academy of Sciences. http://nobelprize.org/nobel_prizes/chemistry/laureates/2010/press.html. Retrieved 6 October 2010 .
3. ^ Richard F. Heck (1968). "Acylation, Methylation, and Carboxyalkylation of Olefins by Group VIII Metal Derivatives". Journal of the American Chemical Society 90: 5518. doi:10.1021/ja01022a034.
4. ^ Richard F. Heck (1968). "The arylation of allylic alcohols with organopalladium compounds. A new synthesis of 3-aryl aldehydes and ketones". J. Am. Chem. Soc. 90 (20): 5526–5531. doi:10.1021/ja01022a035.
5. ^ Richard F. Heck (1968). "Allylation of aromatic compounds with organopalladium salts". J. Am. Chem. Soc. 90 (20): 5531–5534. doi:10.1021/ja01022a036.
6. ^ Richard F. Heck (1968). "The palladium-catalyzed arylation of enol esters, ethers, and halides. A new synthesis of 2-aryl aldehydes and ketones". J. Am. Chem. Soc. 90 (20): 5535–5538. doi:10.1021/ja01022a037.
7. ^ Richard F. Heck (1968). "Aromatic haloethylation with palladium and copper halides". J. Am. Chem. Soc. 90 (20): 5538–5542. doi:10.1021/ja01022a038.
8. ^ Richard F. Heck (1968). "The addition of alkyl- and arylpalladium chlorides to conjugated dienes". J. Am. Chem. Soc. 90 (20): 5542–5546. doi:10.1021/ja01022a039.
9. ^ Richard F. Heck (1968). "A synthesis of diaryl ketones from arylmercuric salts". J. Am. Chem. Soc. 90 (20): 5546–5548. doi:10.1021/ja01022a040.
10. ^ Tsutomu Mizoroki, Kunio Mori and Atzumu Ozaki (1971). "Arylation of Olefin with Aryl Iodine Catalyzed by Palladium". Bull. Chem. Soc. Japan 44 (2): 581. doi:10.1246/bcsj.44.581.
11. ^ R.F. Heck and J.P Nolley, Jr. (1972). "Palladium-catalyzed Vinylic Hydrogen Substitution Reactions with Aryl, Benzyl, and Styryl Halides". The Journal of Organic Chemistry 37 (14): 2320–2322. doi:10.1021/jo00979a024.
12. ^ Richard F. Heck (1982). "Palladium-Catalyzed Vinylation of Organic Halides". Organic Reactions 27. doi:10.1002/0471264180.or027.02.
13. ^ J. T. Link (2002). "The Intramolecular Heck Reaction Palladium-Catalyzed Vinylation of Organic Halides". Organic Reactions 60. doi:10.1002/0471264180.or060.02.
14. ^ M. Oestreich, Ed., The Mizoroki-Heck Reaction Wiley (2009)
15. ^ Sonogashira, K; Tohda, Y; Hagihara, N (1975). "A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines". Tet. Lett. 16: 4467. doi:10.1016/S0040-4039(00)91094-3.
16. ^ Heck, Richard F.; Breslow, David S. (1960). J. Am. Chem. Soc. 82: 750. doi:10.1021/ja01488a067.
17. ^ Heck, Richard F.; Breslow, David S. (1961). J. Am. Chem. Soc. 83: 4023. doi:10.1021/ja01480a017.
18. ^ "2006 ACS National Award Winners". Chemical & Engineering News 84 (6): 34–38. 2006-02-06. http://pubs.acs.org/email/cen/html/020906105850.html#5. .
19. ^ "BBC News - Molecule building work wins Nobel". bbc.co.uk. http://www.bbc.co.uk/news/science-environment-11484773. Retrieved October 6, 2010.
20. ^ "Richard F. Heck - Interview". Nobelprize.org. 7 October 2010. http://nobelprize.org/nobel_prizes/chemistry/laureates/2010/heck-telephone.html. Retrieved 7 October 2010.