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Home , Ernst Otto Fischer, Geoffrey Wilkinson, Kurt Alder, Yves Chauvin

hic grap no upplem o s ent M

Ian C. Lennon The impact of in on fine chemicals

IAN C. LENNON REPRINTED FROM Member of chimica oggi/Chemistry Today’s Scientific advisory board chimica oggi/Chemistry Today vol 29 n 3 - 2011

s this is the “2011: International Year of Chemistry” it is many reactions, including asymmetric . The most opportune to reflect on the impact that the Nobel Prize in successful and widely used pharmaceuticals of the last 20 years AChemistry has had on the pharmaceutical and contract have been single enantiomers, such as Lipitor, Plavix and Nexium manufacturing industries. Between 1901 and 2010 the Nobel with combined sales of over $30 Billion in 2009. Therefore it is Prize in Chemistry has been awarded 102 times to 160 Nobel important to acknowledge the contributions of Laureates for achievements in a diverse range of chemistry, for his research into the stereochemistry of organic molecules from polymers to biological chemistry, structural and surface and reactions. Of course we all know the Cahn-Ingold-Prelog Chemistry, to quantum mechanics. This editorial will focus on priority rules. Prelog shared the 1975 prize with , who those Nobel Prizes that have had the biggest impact in the worked on the stereochemistry of enzyme-catalyzed reactions. manufacture of pharmaceuticals and fine chemicals. By the start In the area of peptide chemistry many new drugs could not of the 20th Century chemical manufacturing was well established have been developed without the contributions of Robert Bruce in Europe and many new reactions and techniques were being Merrifield, who invented solid phase peptide synthesis and the developed. The 1902 awarded to Emil famous Merrifield resin. He received his prize in 1984. Fischer for his work on purine and sugar synthesis was highly significant. Fischer has >8 reactions named after him, including In recognizing the impact of fundamental reactions to form new the Fischer Indole synthesis and the Fischer reduction. The 1912 carbon-carbon bonds and extend the scope of , 32 prize was shared between and . the Nobel committee gave the 1979 award to Herbert C. Brown We can all appreciate the impact of the Grignard reaction and for their work developing new boron reagents to enable the synthesis of alcohols and forming new carbon- and phosphorous containing compounds, respectively. The Wittig carbon bonds, but Sabatier’s work on developing methods of reaction is one of the most important and widely applied methods hydrogenating organic compounds in the presence of finely to synthesize double bonds. Over the last twenty years there disintegrated metals, was an equally important milestone in have been many significant Nobel Prizes in Chemistry that have organic chemistry. A few industrial would dispute the impacted organic synthesis. In 1990 the prize was awarded to E. J. fundamental importance of ’s work on the synthesis of Corey, known best for his work on prostaglandin synthesis and the ammonia, which led to the 1918 prize, though awarded in 1919 as CBS reduction. Many of us have a copy of his inspirational tome “The no candidate met the criteria to receive the award in 1918, so it Logic of Chemical Synthesis”. The importance of metal catalyzed was deferred for one year. Haber’s work led to the manufacture of homogenous is highlighted in the following three Nobel fertilizers and explosives, very important during the First World War. Prizes for Chemistry. In 2001 William Knowles, Ryoji Noyori and He was also known as the “Father of chemical warfare”, not an Barry Sharpless shared the prize, Knowles for his pioneering work accolade we would all like to share. in asymmetric hydrogenation, developing the first industrial scale process for L-DOPA; Noyori for the development of the Binap family Can you imagine making complex natural products or of catalysts; and Sharpless for developing asymmetric epoxidation stereochemically congested rings without the Diels-Alder and dihydroxylation reactions. These methods are now used reaction? Otto Paul Hermann Diels and received their routinely in pharmaceutical manufacture. Another methodology Nobel Prize in Chemistry in 1950, followed by in 1954 now widely used for chemical manufacture, is metathesis which for his work on the of the chemical bond and its application was recognized in 2005 when the prize went to , to the elucidation of the structure of complex substances. In Robert H. Grubbs and Richard R. Schrock. Finally, the long overdue the golden era for natural product synthesis that was to follow Nobel Prize in Chemistry, for the most important of carbon-carbon new methods for constructing carbon-carbon bonds and and carbon-hetero atom forming reactions, palladium catalyzed elucidating complex structures transformed chemistry from a cross couplings, was awarded jointly to Richard F. Heck, Ei-ichi science to an art. Arguably, the preeminent organic of Negishi and in 2010. Who has not heard of the Heck the twentieth century Robert B. Woodward received his prize in reaction, the Negishi coupling and the Suzuki coupling? 1965 for outstanding achievements in the art of organic synthesis. Woodward made key contributions to the synthesis and structure “Standing on the shoulders of giants” is a phrase made famous by determination of complex natural products. Major advances in Sir Isaac Newton. It is clear to see how each of the discoveries and were pioneered by advances that has led to Nobel Prizes in Chemistry, has relied upon and and they shared the Nobel Prize for the prior understanding and achievements of earlier chemists, Chemistry in 1973. Wilkinson was well known for the discovery of going back many decades. The technologies highlighted here will the structure of and the invention of Wilkinson’s catalyst, provide the platform for new generations of chemists to continue which led to the development of homogeneous catalysts for expanding the scope of organic synthesis.

Focus on Milestones in Chemistry - supplement to chimica oggi/Chemistry Today - n. 5 September/October 2011 hic grap An interview with... no upplem o s ent M

Gayle De Maria Chemistry at the nursery school to face competition

Gayle De Maria chimica oggi/Chemistry Today [email protected]

“In Italy we should teach chemistry already in the nursery school, in order to fill up the knowledge gap caused by decades of indifference to the science of Alberto Magno and Raimondo Lullo. Only a strong re-launching of this subject could help us to face the competition with other “Science Countries”; Today’s competition, in fact, takes place, in most part, on the chemical field”. This is the beginning of an interview, held by the Italian newspaper “Avvenire” on May 19th 2011, to Enrico Drioli, professor of Chemistry at the department of Chemical Engineering and Materials at the University of Calabria. chimica oggi /Chemistry Today journal on the occasion of the International Year of Chemistry and of its issue on “Milestones in Chemistry” thought it could be interesting to contact directly Drioli to have a few comments on the topic “Chemistry in Italy” from an Italian expert involved in many international societies and editorial boards.

ENRICO DRIOLI 33 Department of Chemical Engineering and Materials, University of Calabria, via Pietro Bucci, cubo 44A, 87036 Rende (CS), Italy Institute on Membrane Technology (ITM–CNR), via Pietro Bucci, cubo 17C, 87036 Rende (CS), Italy phone + 39 0984 492039 fax + 39 0984 492039 e-mail [email protected]; [email protected]

Educatione and ... 1965 Graduated in Chemistry, University of Naples 1968-1982 Professor of Chemistry and Electrochemistry at the School of Engineering of the University of Naples 1982-1985 Dean of the School of Engineering of the University of Calabria Since 1981 Full Professor at the School of Engineering of the University of Calabria Since 2010 WCU (World Class University) Distinguish Visiting Professor, Department of Energy Engineering, Hanyang University, Seoul Korea Since 2011 Founding Director of the Institute on Membrane Technology

Main Research Activities - Membrane Science and Engineering - Membranes in Artificial Organs - Integrated Membrane Processes - Membrane Preparation and Transport Phenomena in Membranes - Membrane Distillation and Membrane Contactors - Catalytic Membrane and Catalytic Membrane Reactors

Scientific activity His research activities focus on membrane science and engineering. He received awards and honors. Among them: Doctorate Honoris Causa from the University of Paul Sabatier of Toulouse; International Cooperation Honor Award given by the Membrane Industry Association of China for his special dedication to the International Cooperation between China and Europe in the field of membrane and science technology; Guest Professor in the Environment and Safety Engineering Department at the Jiangsu Polytechnic University, China; honorary member of the A. V. Topchiev Institute of Petrochemical Synthesis at the Russian Academy of Sciences, Moscow; Doctorate Honoris Causa in Chemistry and Chemical Technology from the Russian Academy of Science; and honorary professor at the China Northwest University in Xi’an, Shaanxi, People’s Republic of China. He is involved in many International Societies, Scientific Committees, Editorial Boards, and International Advisory Boards. He is currently Chairman of the Section on “Membrane Engineering” of the European Federation of Chemical Engineering. He is author of more than 600 scientific papers, 18 patents and Editor of 18 books in the field of Membrane Science and Technology.Focus on Milestones in Chemistry - supplement to chimica oggi/Chemistry Today - n. 5 September/October 2011 Why is Italy not so attractive for a young researcher? at the elementary school, in the appropriate form, might be a Is it due to money or is there another reason? solution. Researchers and young researchers in particular have never This concept has been very well understood also in Europe been and are not motivated by money and I am not really Unfortunately we are doing just the opposite. We are reducing sure that our young generations don’t see any attraction for more and more also the teaching of chemistry in the High School. research. The situation is different. Italy is one of the Country with the lowest number of available positions for researchers In the new technical research areas that are growing in the East compared to all the industrialised Country worldwide. and Middle East chemistry is taking the role of queen science. The lack of opportunities to make research in a decent How is Italy participating to this awakening? atmosphere and with a decent salary is creating the situation Italian Researchers are present in the most advanced of today: a smaller number of researchers and in average research laboratories in many places around the world and older than in other countries. In the last few years at the CNR, their contributions is often very well recognised. However their in particular, a certain increase in the offering of new positions presence is not related to any strategic vision in the Country. particularly in the South has been taking place. Their return home after important experiences abroad is often However we are far away from the real necessity of the Country. difficult or impossible.

According to you, why our University places itself at 100th Why in Italy the refusal of Chemistry is getting stronger position in the world ranking while we are at the 8th place (even as education)? concerning world power? Our System does not recognise and does not understand the We are still a Country producing goods of high quality in central role of the scientific knowledge on the progresses of our various areas. However we are losing more and more positions industrial world and of the overall quality of our life. particularly in fields of strategic interest for the future where the contribution of the scientific progress is fundamental. Moreover What kind of education and knowledge do you need to remove the Italian capability for innovation is still present and hundreds the suspicious around Chemistry? of small-medium size industries have been able to compete at Understanding the central role of sciences and of the international level. technology for the progresses of our Society is the key point. The “Italy System” is largely absent in these successes, and this The suspicious around chemistry is just a lack of understanding might explain the position of our Universities in the International and knowledge. evaluations. In other Countries the role of the University and its visibility is well present in the Society. The is also characterized by severe We, particularly from a political level, don’t have the same accidents… attention and understanding of the role of the “human capital” Severe accidents happened and might happen in any 34 today. production system, in any human activity. To attribute them just to the Chemistry is again a generalised lack of understanding As you have been teaching for a long time, could you tell us and of knowledge. how you consider the preparation of the first-year students? And when they graduate? Why green chemistry has not reached a high degree of Could you compare the preparation of today’s students with diffusion? the students of previous years? Significant efforts have been carried on in the past yearsto The potential quality of our students is in general good and razionalize industrial productions and to realize a sustainable often excellent compared to the ones in other countries. growth. A large number of people, however, are not aware of the However the level of their real knowledge when entering the huge progresses realized in recent years in process engineering University is dramatically lower compared to the ones of 10-20 in general and in the minimization of the environmental impacts years ago. And their understanding of the role of education of the modern Society. is unfortunately not really significant.No one is considering China, Korea, and various other countries are taking more and University as the “Engine of Country”, as it happens more a leadership in an aggressive strategy in order to improve in many other parts of the world. industrial productions, combined with advanced clean technologies in their production lines. Chemistry? Let’s start from the nursery school. International laboratories have been created, and new In our modern Society the participation of initiatives will appear in the next few years addressed to the citizens to the major aspects of our life is realization of an industrial sustainable growth. growing significantly. A large number of Worldwide the problem is very well understood and in people are interested and aware general appropriate strategies have been or are going to be of problems related to implemented. the environment, to energy, to quality What are the researches that will lead to a new era of Chemistry? of food and to The strategy of process intensification in which Europe has our health, etc. a leadership, might significantly contribute to the solution or But the growth minimization of the problems. of participation has The Skyline Delft Debates in progress today are a good example to be accompanied by a of European attention to these aspects. However, particularly growth in education and in our Country, the visibility and the interest for the real work in particularly in scientific progress is unfortunately quite modest, compared to the one in education. Starting other industrial Countries. This phenomena is directly related to to teach science and the lack of investments in high education and in science and chemistry in particular, technology.

Focus on Milestones in Chemistry - supplement to chimica oggi/Chemistry Today - n. 5 September/October 2011 hic grap no upplem o s ent M

Oliver Briel The impact of precious metals chemistry in the evolution of modern societies

to be printed in OLIVER BRIEL chimica oggi/Chemistry Today vol 29 n 6 - 2011 Member of chimica oggi/Chemistry Today’s Scientific advisory board

he “2011: International Year of Chemistry” allows me appeared, namely the Ziegler-Natta and the Philips and my colleagues from the scientific advisory board process for polypropylene and polyethylene production T of Chimica Oggi/Chemistry Today to reflect on the involving early transition metals (4), as well as the Monsanto influence of advances in chemistry research during the process using a Rhodiumcarbonyl catalyst for Acetic Acid past 109 years by looking at who was awarded with the production (5), or, manufacture of oxo-alcohols by use Nobel Prize in Chemistry and which socio-economic impact of and Rhodium complexes as hydroformylation did the research contributions of the Laureates have. catalysts (6) or the Wacker Process for the direct oxidation As a representative of a precious metals company I will of ethylene to name the most significant ones. Far more logically take a look at it in the perspective of precious than 10 Mio tons of these products are synthesized annually, metals chemistry. Just recently, in the May issue of 2011 my involving Precious Metals complexes acting as catalysts. colleague Ian C. Lennon did a formidable job highlighting We should not forget to mention one of the more recent the impact of Nobel Prize in Chemistry on fine chemicals (1). Laureates, , who was awarded the Nobel Amongst others he mentioned three recent important Nobel Prize in 2007 for “his studies of chemical processes on solid Prizes which for sure are still in everybody’s mind: 2010 Nobel surfaces” (7). Starting already in the 1960s his fundamental Prize was jointly awarded to Richard F. Heck, Eichi Negichi work towards understanding thermodynamics and kinetics and Akira Suzuki for their contributions to developing the on solid surfaces heavily influenced development and technology of Palladium catalysed coupling reactions. design of heterogeneous Platinum Group Metals (PGM) 2005 prize was awarded to Yves Chauvin, Robert H. Grubbs catalysts. Besides synthesis of petrochemicals and fine 35 and Richard R. Schrock for their contributions in the field of chemicals making use of catalysts such as Pt/Al2O3 or Pd/C and in 2001 it was awarded to William S. the most important application involving a heterogeneous Knowles, Ryoji Noyori and K. Barry Sharpless for their work in Precious Metals catalyst is certainly emission control for developing methodologies to catalytically and selectively combustion engines. Today, almost every vehicle carries a build up chiral centres in organic molecules. Note that catalytic converter reacting harmful mixtures of off gases almost all of these methodologies make use of precious into nearly clean air. The constant tightening of emission metals underlining their importance in new synthetic regulations requires substantial efforts in the continuous methods for manufacturing fine chemicals. It is also worth improvement of catalyst design. mentioning that these recent Laureates were honoured for Statistics say that there are some 600 Mio motor vehicles their contributions to modern synthetic methods employing operating in the world today. Assuming each car is homogeneous catalysis. equipped with an exhaust catalyst with an average of 5g Some thirty years earlier, in 1973 Ernst Otto Fischer and PGM loading, it totals to the astonishing number of 3.000t Sir Geoffrey Wilkinson were awarded the Nobel Prize "for PGM’s (mainly Platinum, Palladium and Rhodium) that are their pioneering work, performed independently, on the driving around on our earth. Having in mind PGM’s being chemistry of the organometallic, so called sandwich scarce and very costly to extract from ores it is obvious that compounds”. Both chemists had significantly powerful recycling and recovery processes are needed contributed to develop the field of transition when it comes to the end of life of a vehicle. metals complex chemistry (2, 3), laying the In fact, Precious Metals and their chemistries foundation of a rather new field in have an outstanding importance towards catalysis, homogeneous catalysis. the development of modern Soon after their initial discoveries civilizations and a long history. in 1952 first industrial processes Starting already during

Focus on Milestones in Chemistry - supplement to chimica oggi/Chemistry Today - n. 5 September/October 2011