André Lubineau: a life dedicated to carbohydrate chemistry
Published:20 Mar 2014
Y. Queneau, J. Augé, G. Descotes, and D. Bonnaffé, in Carbohydrate Chemistry: Chemical and Biological Approaches, Volume 40, ed. A. Pilar Rauter, T. Lindhorst, and Y. Queneau, The Royal Society of Chemistry, 2014, vol. 40, pp. P011-P014.
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The aim of this volume 40 of Carbohydrate Chemistry, Chemical and Biological Approaches is to illustrate how wide is the scope of carbohydrate chemistry, from synthetic methodology to chemical biology, and to acknowledge Professor Lubineau's contributions to the field.
André Lubineau was born on June 12, 1943 in Paris. He was soon interested by chemistry and entered the well-known Ecole Nationale Supérieure de Chimie de Paris. After his diploma in 1966, he was appointed as an assistant teacher in the university of Paris-Sud, Orsay where he concomitantly pursued doctoral studies in the field of nucleosides, under the guidance of Professor Serge David, a great figure of carbohydrate chemistry who has passed away last year (1921–2013). After having graduated as Docteur ès Sciences in 1973, André Lubineau together with Serge David then embraced a new field in the laboratory, i.e. the exploration of hetero Diels-Alder reaction as a new tool to build dihydropyrans. Successfully applied to the formation of disaccharides starting from a monosaccharide dienyl ether, this strategy was a breakthrough in asymmetric cycloadditions in which the chiral induction was brought by a chiral diene. They developed this method to build the d-galacto unit of the antigenic blood groups, such as the A trisaccharide, on the gram scale. This was the beginning of a long story concerning the synthesis of oligosaccharides of biological interest, in close collaboration with Professor Ten Feizi, at Harrow Hospital, England.
In 1979, interested in widening his knowledge in new methodologies and total synthesis, André Lubineau's joined for one year the group of Professor Barry M. Trost in Madison, Wisconsin. After returning to Orsay and being appointed as Assistant Professor then Full Professor, he started his research on the use of water as solvent for cycloadditions. He succeeded rapidly in this field and was able to propose a new paradigm, i.e. all reactions with a negative activation volume should be prone to be accelerated in water. Confirmed in the case of other reactions such as aldolisation, Michael and Baylis-Hillman reactions, the acceleration was demonstrated to originate mainly from an entropic effect. Though green methodologies were at that time not as fashionable as they are today, he also showed strong interest for carbohydrate-based synthons and chemicals.
In the mid 1980's, André Lubineau and his team joined a mixed academic-industrial consortium which evolved from an initial collaboration between the University of Lyon and the sugar company Béghin-Say under the auspices of the CNRS. This consortium gathered carbohydrate chemists located in the universities of Bordeaux, Clermont-Ferrand, Grenoble, Lille, Lyon, Orsay and Poitiers, as well as industrial researchers specialised in chemical and biotechnological sugar processes. It was also at this time that, in a friendly and stimulating thematic community including groups such as those of L. Hough and F. W. Lichtenthaler, the meetings “Carbohydrates as organic Raw Materials” on innovative processes (ultrasound, microwaves, electrochemistry, enzymes…) and industrial applications (detergents, emulsifiers, polymers, food additives…) took place in Darmstadt, Lyon, Wageningen and Vienna. The presence of André Lubineau with his exceptional experience and his contagious positive spirit was precious to these meetings and to the collaborative work achieved within the French consortium. André's permanent joviality and friendly availability impressed all colleagues during this 10-year collaboration. We associate all former members of this group, notably their founders and friends of André's: Alain Bouchu, Jacques Defaye, Alain Deffieux, Bernard Fournet, Jacques Gélas, Claude Lamy, Julio Mentech, André Mortreux, Serge Perez and Bernard Thiriet.
From this time, while also deeply involved in projects related to biological applications, André Lubineau never stopped being interested in the industrial side of glycochemistry. Actually, for both types of projects, he followed the same strategy, always looking for solutions to problems, not for problems to solutions, always asking: is this new, is this useful?
The chemoenzymatic approaches Serge David and André Lubineau developed with Claudine Augé and Christine Le Narvor are perfect illustrations of the way he conceived challenges in organic synthesis, especially for the total syntheses of bioactive oligosaccharides: “use chemistry when it is the most efficient route and enzymes when they do the job better”. If no clear option was obvious, both methods were explored convinced that the answers would be precious to future generation of glycochemists. This even led to a contest in the lab for determining the most efficient access to sialic acid, either by extraction from edible swallow's nests, (enjoyed by André who was a gourmet), or by aldolisation of N-acetyl-d-mannosamine using sialylaldolase. At that time, extracting sufficient amounts of glycosyltransferases for the synthesis of an oligosaccharide on the multi-milligram “chemist scale” was a tedious and time consuming work. Together with the late André Verbert, André Lubineau met the challenge and promoted an interdisciplinary consortium on Recombinant GlycosylTransferases (the GTREC) and within few years, recombinant α-2,6- and α-2,3-sialyltransferases and α-1,3/4-fucosyltransferase were available in Orsay, giving the group a decisive advantage in the synthesis of Lewis type antigens at the origin of seminal discoveries in the field together with Ten Feizi. In the selectin domain, thanks to his chemist's eye which considered a sulphate group mimicking the carboxylate moiety of sialic acid, he foresaw that the sulphated versions of the Lewis antigens identified by glycobiologists were not artefacts and demonstrated, through unambiguous total synthesis, that 3′-sulfo-Lewis was the most potent ligand of E-Selectin known at that time.
From sulphated Lewis antigens to glycosaminoglycans (GAG), the path may seem straightforward. However, addressing the challenge of GAGs molecular diversity was like finding a needle in a haystack, and for André Lubineau, the answer should arise from modern developments in organic synthesis. At that time, combinatorial synthesis was rising and André was among the first ones to think about applying this strategy for designing complex oligosaccharides. Twenty years later, this paradigm has been well established although much work remains to be done: this offers good reasons to follow André Lubineau's determination to invent new chemistries able to offer solutions to the exciting challenges faced by carbohydrate chemists.
In addition to his scientific legacy, André Lubineau will be remembered as a charismatic pedagogue and a demanding and rewarding mentor by his students. Always pushing them to widen their scientific culture while continuingly digging deeper into their field to reach the best possible level once they fly with their own wings, encouraging them to take risks as he always did throughout his life.
We are extremely grateful to the Specialist Periodic Reports Board and to the Editors of the series Carbohydrate Chemistry, Professor Amelia P. Rauter and Thisbe K. Lindhorst, for their kind invitation to elaborate this book dedicated to the memory of Professor Lubineau. We thank all the authors who have contributed to this volume, and we also associate in this tribute all other André's former friends, colleagues and students who could not join on this occasion.