Suzuki, Nobel prize

In 1912 a Polish scientist C. Prank pnblished a paper in Journal of Physiology, in which he also reported an extracted compound from rice bran with the same procedure as Suzuki reported and named the extracted substance Vitamin (which means vital amine). The componnd is the same as that found by Suzuki. The Nobel Prize for Medicine and Physiology in 1929 was awarded to C. Eijkman and F. G. Hopkins for their discovery and contributions to Vitamin, but it is obvious that the discoverer of Vitamin is Suzuki. Vitamin A was isolated in 1914, four years after the discovery of Oryzanin (Vitamin Bf). 

Organometallic chemistry has been a popular subject for the Nobel prize committee. In 1912 Grignard (Mg) won the award, in 1973 Wilkinson and Fischer for sandwich compounds (such as ferrocene), in 2005 Chauvin, Grubbs, and Schrock for alkene metathesis, and in 2010 Fleck, Negishi, and Suzuki (Stille had died in 1989) for transition-metal catalysed couplings. 

The cross-coupling reactions developed over the past 50 years have now been recognized by Nobel prizes to Heck, Suzuki, and Negishi. The relevance of these reactions in synthesis is obvious by the enormous number of publications dealing with the applications for the formation of sp carbon to sp carbon bond formation. Perhaps for this reason, only a few examples will be presented here, as the cycloheptanoid skeleton is basically made up of sp carbon atoms. Certainly, the inherent creativity of the synthetic organic chemist will change this situation very soon. 

Heck, R. F. NoUey, J. P., Jr. J. Am. Chem. Soc. 1968, 90, 5518-5526. Richard Heck discovered the Heck reaction when he was Hercules Corp. Heck won Nobel Prize in 2010 along with Akira Suzuki and Ei-ichi Negishi for palladium-catalyzed cross couplings in organic synthesis . 

Robert F. Heck shared the 2010 Nobel Prize in Chemistry with Ei-iohi Negishi and Akira Suzuki for development of palladium-catalyzed cross coupling reactions. 

Among these reactions, three were recognized with a Nobel Prize in Chemistry in 2010. The Nobel Prize was awarded on the basis of practical use in the industrial sector. Heck reactions were used for the synthesis of more than 100 kinds of natural products and physiologically active substances, Negishi reactions were used for the synthesis of pumiUotoxins A (PTXs) and hennoxazole A, and Suzuki-Miyaura reactions were used for the syuthesis of dynemicin A and dragmacidin F [ 100,101]. 

The Suznki reaction is an important C-C bond-forming reaction of an aryl- or vinylboronic acid (112) with an aryl- or vinylhaUde (111, 115), catalyzed by a pal-ladinm(0) complex. Recently, Akira Suzuki won the 2010 Nobel Prize in chanistry for his significant contribution and development of this reaction. The literature survey reveals several modifications to the reaction. The application of various ZnO-supported metal combinations such as Pd-Ag, Pd-Cu, Pd-Ni, and Pd (Kim and Choi 2009) were reported for the cross-coupling Snzuki reaction between aryl halides (111, 115) and phenyl boronic acid (112) (Schemes 9.34, 9.35). These metal combinations with ZnO resulted in excellent yields of the biaryl products. 

In 2010, Richard Heck, Ei-ichi Negishi, and Akira Suzuki shared the Nobel Prize in Chemistry for their work on C—C coupling reactions. 

Scheme 7.16. Some examples of the Suzuki reaction. The process permits creation of carbon-carbon bonds by coupling of alkyl, alkenyl, and aryl halides (I > Br Cl) with organoboron compounds. Akira Suzuki, Ei-ichi Negishi and Richard Heck shared the Chemistry Nobel Prize in 2010.

The palladium-catalyzed Suzuki-Miyaura reaction is a cross-coupling reaction between aryl halides and horon derivatives (Scheme 19.40) [54]. Snznki received the Nobel Prize in 2010 [54h]. Reactions are performed under mild conditions and many functional gronps are tolerated. Water is not a problem and may be even beneficial (vide infra). The first reported reactions hy Suzuki in 1979 insisted about the presence of a base, even if no proton is exchanged [54a, b]. Various bases have been used EtO, MeO", OH", CO ", and F" associated with countercations such as Na, K% Cs+, LP, nBu N+, Ag+, or TP [54, 55]. The role of the base has led to many mechanistic interpretations involving among them anionic arylborates as reagents [54g, 56]. 

The Suzuki-Miyaura reaction is perhaps one of the most well-known coupling protocols developed to date. A seareh of the literature reveals over 15000 citations to work employing this eoupling protocol that was first developed in 1979 and for whieh Akira Suzuki shared the Nobel Prize in Chemistry in 2010. The two seminal papers in 1979 co-authored by Suzuki and Miyaura deseribe the eross-eoupling of vinyl boronic acids with vinyl bromides (Scheme 13.1) or aryl halides (Scheme 13.2), employing 1 mol.% tetrakis(triphenylphosphene)palladium and a base such as sodium ethoxide. The stereoselectivity of the reactions was excellent with >99% retention of double bond geometry. The evolution of the various Suzuki coupling partners is shown in Scheme 13.3. 

As a final comment, although restricted in its essence to palladium chemistry - but which is nonetheless at the heart of modern cross-coupling arylation reactions - we quote from Astruc [12i], in conclusion, the field of palladium-catalyzed cross-coupling reactions for their work in which Heck, Negishi, and Suzuki were awarded the 2010 Nobel Prize in chemistry is extremely rich and productive and will continue to grow with major synthetic applications and green implications in the future. ... 

The 2010 Nobel Prize in Chemistry was awarded to Richard F. Heck (University of Delaware), Ei-ichi Negishi (Purdue University), and Akira Suzuki (Hokkaido University) for their work on paiiadium-cataiyzed cross-coupiing reactions. Eariy and important contributions were made by John Stille (Colorado State University) before his untimely death in a 1989 plane crash. 

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