Sharpless, Nobel prize

Enantioselectivity. In 1980, T. Katsuki and K. B. Sharpless (Nobel Prize, 2001) reported a method whereby prochiral allylic alcohols are epoxidized in the presence of r-BuOOH, Ti(/-OPr)4, and (-h)-or (-)-diethyl tartrate (DET) with high regio- and stereoselectivity to produce the corresponding optically active epoxides." ... 

Dr. K. Barry Sharpless, Nobel Prize Laureate, after losing an eye in a cryogenic explosion ... 

For developing osmium catalyzed oxidation methods for preparing chiral com pounds of high optical pu rity Professor K Barry Sharpless (Scripps Research Institute) shared the 2001 Nobel Prize in chemistry... 

For his work on chirally catalyzed oxidation reactions, representing a major contribution to the development of catalytic asymmetric synthesis, K. B. Sharpless was awarded the Nobel Prize for chemistry in 2001. ... 

A different approach to making chiral drugs is asymmetric synthesis. An optically inactive precursor is converted to the drug by a reaction that uses a special catalyst, usually an enzyme (Chapter 11). If all goes well, the product is a single enantiomer with the desired physiological effect In 2001, William S. Knowles, Ryogi Noyori, and K. Barry Sharpless won the Nobel Prize in chemistry for work in this area. 

In 1980, K. B. Sharpless (then at the Massachusetts Institute of Technology, presently at the University of California San Diego, Scripps research Institute co-winner of the Nobel Prize for Chemistry in 2001) and co-workers reported the Sharpless asymmetric epoxidation . 

The standard work of Evans [2] as well as a survey of the papers produced in the Journal of Labeled Compounds and Radiopharmaceuticals over the last 20 years shows that the main tritiation routes are as given in Tab. 13.1. One can immediately see that unlike most 14C-labeling routes they consist of one step and frequently involve a catalyst, which can be either homogeneous or heterogeneous. One should therefore be able to exploit the tremendous developments that have been made in catalysis in recent years to benefit tritiation procedures. Chirally catalyzed hydrogenation reactions (Knowles and Noyori were recently awarded the Nobel prize for chemistry for their work in this area, sharing it with Sharpless for his work on the equivalent oxidation reactions) immediately come to mind. Already optically active compounds such as tritiated 1-alanine, 1-tyrosine, 1-dopa, etc. have been prepared in this way. 

For a related complex, see W. V. Konze, B. L. Scott, and G. J. Kubas, J. Am. Chem. Soc. 124 (2002), 12 550 Bill Knowles shared the 2001 Nobel Prize (with Barry Sharpless and Ryoji Noyori) for his development of catalytic asymmetric hydrogenation. 

The asymmetric hydrogenation of cinnamic acid derivatives has been developed by Knowles at Monsanto [4], The synthesis of L-dopa (Figure 4.3), a drug for the treatment of Parkinson s disease, has been developed and is applied on an industrial scale. Knowles received the Nobel Prize for Chemistry in 2001 together with Noyori (see below, BINAP ) and Sharpless (asymmetric epoxidation). 

I. Noyori, R. Ohta, M. Hsiao, Y. Kitamura, Ma. Ohta, T. Takaya, H. J. Am. Chem. Soc. 1986, 108, 7117. Ryoji Noyori (Japan, 1938—) and Herbert William S. Knowles (USA, 1917—) shared half of the Nobel Prize in Chemistry in 2001 for their work on chirally catalyzed hydrogenation reactions. K. Barry Sharpless (USA, 1941—) shared the other half for his work on chirally catalyzed oxidation reactions. 

Excerpt 4F is taken from an article written by Demko and Sharpless. (Barry Sharpless was a co-recipient of the Nobel Prize in Chemistry in 2001 for his work on chirally catalyzed oxidation reactions.) In this article, the authors propose a way to synthesize aromatic tetrazoles from nitriles in water, using only sodium azide and a zinc salt. Water, despite its obvious advantages (i.e., safe and inexpensive), rarely succeeds as a solvent in organic synthesis. Thus, a synthesis that uses water successfully is an important scientific accomplishment. 

K. Rudzka, A. M. Arif and L. M. Berreau, Inorg. Chem., 44, 7234 (2005). http //nobelprize.org/nobel prizes/chemistry/laureates/2001/sharpless-lecture.pdf. 

One of the success stories of transition metal catalysis is the rhodium-complex-catalyzed hydrogenation reaction. Asymmetric hydrogenation with a rhodium catalyst has been commercialized for the production of L-Dopa, and in 2001 the inventor, Knowles, together with Noyori and Sharpless, was awarded the Nobel Prize in chemistry. After the initial invention, (enantioselective) hydrogenation has been subject to intensive investigations (27). In general, hydrogenation reactions proceed... 

Indeed, several interesting procedures based on three families of active catalysts organometallic complexes, phase-transfer compounds and titanium silicalite (TS-1), and peroxides have been settled and used also in industrial processes in the last decades of the 20th century. The most impressive breakthrough in this field was achieved by Katsuki and Sharpless, who obtained the enantioselective oxidation of prochiral allylic alcohols with alkyl hydroperoxides catalyzed by titanium tetra-alkoxides in the presence of chiral nonracemic tartrates. In fact Sharpless was awarded the Nobel Prize in 2001. 

The selective oxidation of hydrocarbons, particularly that of alkanes, remains a challenge. It is not surprising, therefore, that the problems of oxidation processes are addressed in several books,1043-1045 reviews,1046-1057 and a journal special issue,1058 as well as in international conferences1059-1064 devoted to the topic. For the advances in chirally catalyzed oxidation processes, including asymmetric epoxidation and osmylation, Sharpless was one of the recipients of the 2001 Nobel Prize in Chemistry. 

Osmium-catalysed dihydroxylation of olefins is a powerful route towards enantioselective introduction of chiral centers into organic substrates [82]. Its importance is remarkable because of its common use in organic and natural product synthesis, due to its ability to introduce two vicinal functional groups into hydrocarbons with no functional groups [83]. Prof. Sharpless received the 2001 Nobel Prize in chemistry for his development of asymmetric catalytic oxidation reactions of alkenes, including his outstanding achievements in the osmium asymmetric dihydroxylation of olefins. 

The Nobel Prize in Chemistry 2001 was awarded to three researchers for their pioneering work in the field of asymmetric catalysis. One of them, K. Barry Sharpless, was honored for the epoxidations named after him (Section 3.4.6). The second reason for the award was his development of the asymmetric dihydroxylation (AD Figure 17.21). The Sharpless reactions that were honored with the Nobel Prize have three things in common first, they are oxidations, second, they are catalytic asymmetric syntheses, and third, they owe their high enan-tiocontrol to the additive control of stereoselectivity. In the introductory passages to... 

The 2001 Nobel Prize in chemistry was shared by W. S. Knowles, who developed these chiral hydrogenations at Monsanto R. Noyori, who also worked in the area of chiral hydrogenations and K. B. Sharpless, who developed methods for chiral epoxi-dation reactions. 

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