Richard Frederick Heck (August 15, 1931 – October 9, 2015) was an American chemist noted for the discovery and development of the Heck reaction, which uses palladiumtocatalyzeorganic chemicalreactions that couple aryl halides with alkenes. The analgesic naproxen is an example of a compound that is prepared industrially using the Heck reaction.
During the early 1970s, Tsutomu Mizoroki independently reported the use of the less toxic aryl halides as the coupling partner in the reaction.[7][8] Heck became a professor of chemistry at the University of Delaware's Department of Chemistry and Biochemistry in 1971, where he continued to improve the transformation, developing it into a powerful synthetic method for organic synthesis.[3]
The importance of this reaction grew as it was taken up by others in the organic synthesis community.[9][10] In 1982, Heck was able to write an Organic Reactions chapter that covered all the known instances in just 45 pages.[11] By 2002, applications had grown to the extent that the Organic Reactions chapter published that year, limited to intramolecular Heck reactions, covered 377 pages. These reactions, a small part of the total, couple two parts of the same molecule.[12]
The reaction is now one of the most widely used methods for the creation of carbon-carbon bonds in the synthesis of organic chemicals. It has been subject to numerous scientific review articles, including a monograph dedicated to this subject published in 2009.[13]
Heck's contributions were not limited to the activation of halides by the oxidative addition of palladium. He was the first to fully characterize a π-allyl metal complex,[4] and the first to elucidate the mechanism of alkene hydroformylation.[5]
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; the reaction also allows biologically important proteins to be tracked.[16][17] 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.[18]
Heck retired from the University of Delaware in 1989, where he became the 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.[19][20] On October 6, 2010, the Swedish Royal Academy of Sciences awarded Heck the Nobel Prize in Chemistry, which he shared with Ei-ichi Negishi and Akira Suzuki "for palladium-catalyzed cross couplings in organic synthesis".[1][21][22] In 2011, Heck was awarded the Glenn T. Seaborg Medal for this work. In 2012, he was appointed by De La Salle UniversityinManila as an adjunct professor in its chemistry department. He had moved to Quezon City, Philippines after retirement, with his wife, Socorro Nardo-Heck. The couple had no children.[23][24]
Heck died on October 9, 2015, in Manila in a public hospital. His wife predeceased him by 2 years.[25][26]
^ abcNegishi, Ei-Ichi (1999). "A profile of Professor Richard F. Heck". Journal of Organometallic Chemistry. 576 (1–2): xv–xvi. doi:10.1016/S0022-328X(98)01136-X.
^ abHeck, Richard F.; Breslow, David S. (1960). "Allylcobalt Carbonyls". Journal of the American Chemical Society. 82 (3): 750–751. doi:10.1021/ja01488a067.
^ abHeck, Richard F.; Breslow, David S. (1961). "The Reaction of Cobalt Hydrotetracarbonyl with Olefins". Journal of the American Chemical Society. 83 (19): 4023–4027. doi:10.1021/ja01480a017.
^Heck, Richard F. (1968). "Acylation, methylation, and carboxyalkylation of olefins by Group VIII metal derivatives". Journal of the American Chemical Society. 90 (20): 5518–5526. doi:10.1021/ja01022a034. and six further articles, pages 5526–5548
^Heck, R. F.; Nolley, J. P. (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.
^Beletskaya, Irina P.; Cheprakov, Andrei V. (2000). "The Heck Reaction as a Sharpening Stone of Palladium Catalysis". Chemical Reviews. 100 (8): 3009–3066. doi:10.1021/cr9903048. PMID11749313.
^Mc Cartney, Dennis; Guiry, Patrick J. (2011). "The asymmetric Heck and related reactions". Chemical Society Reviews. 40 (10): 5122–5150. doi:10.1039/C1CS15101K. PMID21677934.
^Johansson Seechurn, Carin C. C.; Kitching, Matthew O.; Colacot, Thomas J.; Snieckus, Victor (2012). "Palladium-Catalyzed Cross-Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize". Angewandte Chemie International Edition. 51 (21): 5062–5085. doi:10.1002/anie.201107017. PMID22573393.
^Harrington, Peter J.; Lodewijk, Eric (1997). "Twenty Years of Naproxen Technology". Organic Process Research & Development. 1: 72–76. doi:10.1021/op960009e.
