► Well done Laurent Gillard! You did it. Laurent successfully achieved his PhD thesis entitled "Towards the Total Synthesis of Manzaminoids", under the finaly supervision of professor Ari Koskinen (Aalto University) and professor O.Riant (UCLouvain).
Short abstract : "This thesis focused on the conception of new potential bioactive manzamine derivatives. For this purpose, new molecules were synthetized using novel approaches of anionic polycyclization. Three methodologies were developed allowing to reach our targets, and some mechanistical analyses were made to rationalize the diastereoselectivity. Finally, the derivatisation of some target molecules allowed us to quickly extend our library of bioactive compounds."
► Great job Jean-François Body! You did it. Jean-François successfully achieved his PhD thesis entitled "Development of Methodologies towards the Total Synthesis of Okadaic Acid".
Short abstract :"During the last decades, our laboratory has been interested in the development of new synthetic methodologies and their application to the total syntheses of natural products exhibiting biological activities. In this context, this work started with an investigation of the diastereoselective parameters of the ISMS reaction (Intramolecular Silyl Modified Sakurai). Three parameters were investigated: (i) the annelating fragment configuration, (ii) the vinylsilane geometry and (iii) the steric hindrance in allylic position. This first part was followed by its direct application to the synthesis of the C15-C27 domain of okadaic acid; a polycyclic ether produced by dinoflagellates. This natural compound exhibits a strong affinity for protein phosphatases 1 and 2A and is largely used as a probe in biochemistry. An unexpected rearrangement during a Woodward-Prevost dihydroxylation triggered our interest and opened doors to the use of photochemistry. Our research finally led to a specific tetracycle containing every chiral centers required to pursue the synthesis of our polycyclic ether. Since green chemistry became an important challenge for chemists all around the world, we decided to develop an electrochemical process leading to the formation of spiroketals. The electrochemical decarboxylation was applied to the synthesis of the C15-C27 domain of okadaic acid and offered a second route towards this fragment. Furthermore, we decided to extend this new and ecological methodology to the synthesis of the C1-C14 and C28-C38. Previous work performed in the laboratory by Dr S. Dochain allowed us to rapidly generate the desired substrate and promoted this wonderful tool."
► Great job Thierry de Merode! You did it. Thierry successfully achieved his PhD thesis entitled "Utilisation de la réaction de Stetter pour la synthèse de bicycles fusionnés".
Short abstract :"Une grande variété de composés naturels contient un squelette interne composé de bicycles voire de polycycles tels que les hydrindanes ou les decalines. Notre laboratoire s’est depuis longtempsintéressé à la synthèse de tels composés et au développement d’une méthodologie générale qui permette une approche synthétique rapide et efficace de ce type de noyaux. Lors de recherches précédemment effectuées dans notre laboratoire, nous avons développé une méthodologie permettant d’accéder à ce type de structure en utilisant comme étape-clé une cyclisation employant une réaction de Stetter. Nous allons donc exemplifier cette méthode."
► Professor passed away, the 31th July 2017. Huge loss for organic chemistry and for the members of his research group.
► Welcome to Guldana and Ernazar. Two students from the University of Astana, Kazakstan, arrived in our laboratory for an internship until mid-August. Welcome to Guldana Issabayeva and Ernazar Kamal.
► Great job Jérôme! Jérôme Savary, one of our PhD student, won the Elsevier Best Poster Prize during the 18th Tetrahedron Symposium : Challenges in Organic Chemistry (28 - 30 June 2017, Budapest, Hungary).
► Le Du, former postdoc in the group since 2015, left. He is headed to China. Farewell.
► Congratulation Thomas Xhurdebise, great job! Thomas Xhurdebise successfully presents his PhD thesis entitled "La Réaction IMSC Appliquée à la Synthèse Stéréosélective de Fragments d’Ethers Polycycliques". He works in the "Polypeptide Group" in Braine-l'Alleuld.
Short abstract :"Les éthers polycycliques sont des métabolites secondaires produits par des micro-algues appartenant à la famille des dinoflagellés. Ces molécules sont souvent de puissantes toxines et provoquent la dévastation de la faune marine ainsi que la contamination des populations côtières dans diverses régions du globe. Au vu de leurs attraits structuraux spectaculaires et de la difficulté à extraire des quantités palpables à partir de sources naturelles, les éthers polycycliques constituent des cibles de choix pour la synthèse totale. En effet, leurs squelettes moléculaires représentent de superbes défis synthétiques et l’accès à de plus grandes quantités permettrait d’étudier plus en détail leur mécanisme d’action. Cette thèse traite de l’usage de réactions intra-moléculaires de type silyl-Prins, regroupées sous le nom général «IMSC» pour «Intramolecular Sakurai Cyclization», pour la synthèse de fragments tricycliques d’éthers polycycliques naturels ou analogues. Ces méthodologies ont été développées dans notre laboratoire il y a plusieurs années et permettent la préparation hautement diastéréosélective de cycles mono-oxygénés. Les aspects configurationnels des produits des réactions IMSC sont similaires à ceux des éthers polycycliques. De ce fait, nos méthodes constituent un outil de choix pour la synthèse rapide et efficace de fragments de ces molécules."
► Welcome to Dylan VELLUT, bachelor from the Institut Paul Lambin (Haute Ecole Da Vinci). He will stay with us until end of June.
► Welcome to Yann RICHARD, bachelor from the Institut Paul Lambin (Haute Ecole Da Vinci). He will stay with us for a period of 3 months.
► Congratulation Pol, great job! Pol Karier successfully presents his PhD thesis entitled "Towards the total synthesis of Amphidinol 3". He is now headed to Norway, to achieve a postdoc.
Short abstract :"Amphidinols are intriguing amphiphilic architectures exhibiting a variety of biological actions, including antifungal, hemolytic, cytotoxic and ichthyotoxic activities. These properties derive from the disturbance of the arrangement of the lipid bilayer of the targeted cells. The third member of the family, amphidinol 3 was discovered in 1996 and is, to date, the only amphidinol whose stereochemistry is fully established (Figure 1). The synthesis of the C13-C30 polyol domain, as well as the preparation of the C31-C40 trans-configured tetraydropyran will be discussed throughout this work".
► Another great news : Jean-François Body (4th year PhD student) won the "Sigma-Aldrich and Dow Award" for the best communication, in the SAS meeting, held in Blankenberge last 8 and 9 December. Well done Jean-François!
► Great news: 3 of our PhD students, who were competing for a funding from the FRIA, got their funding.
Score 3 over 3! Congratulations to Mathilde, Damien and Amaury.
► Welcome to our new PhD students : Mathilde Quertenmont, Amaury Dubart, François Simon and Lei Hu.
► Welcome to the new undergraduate student : Pierre Hubert. He will stay with us in the lab until June 2017.
► Well done! Kevin Debrus; he has achieved successfully his PhD thesis entitled "Nouvelles Méthodologies pour la Préparation de Jérangolides et Analogues".
Short abstract : "Durant cette dernière décennie, une augmentation croissante des infections fongiques a été observée à travers le monde. Ce phénomène provient non seulement de l’augmentation des patients immuno-déficients mais également de la résistance croissante des micro-organismes fongiques vis-à-vis des traitements.
En 1991, les jérangolides naturels A, B, D, E et H ont été isolés et le jérangolide A a révélé des propriétés antifongiques potentiellement intéressantes envers différentes infections fongiques.
Dans le but de développer éventuellement un nouveau médicament antifongique, nous avons décidé de préparer les jérangolides naturels et certains analogues.
Afin de faciliter et accélérer ces synthèses, nous avons développé trois élégantes méthodes de synthèse."
► Congratulations to Coryse Smet; she has achieved successfully her PhD thesis entitled "Vers la synthèse totale de l'halichlorine".
Short abstract :"L’halichlorine, molécule isolée d’une éponge marine, a suscité notre intérêt non seulement pour son activité biologique attrayante, mais également pour le véritable défi que représente sa synthèse. Cet alcaloïde, en inhibant l’induction des VCAM-1 (Vascular Cell Adhesion Molecule-1), pourrait être utile pour le traitement de certains cancers.
Au cours de cette thèse, nous avons progressé de manière significative via une synthèse originale pour atteindre un intermédiaire clé. Dans ce but, plusieurs méthodologies développées au sein de notre laboratoire ont été utilisées, comme la formation d’orthoesters ou encore une réaction de spiroannélation. Diverses autres méthodologies intéressantes ont également fait l’objet de beaucoup d’attentions, dont un réarrangement de Beckmann et une contraction de sulfure d’Eschenmoser".
► Dear Xiaofeng. You finished your 2-years postdoc in our laboratory. You are headed to the United Kingdom. We all wish you the best for your scientific career.
► Welcome to Nathalie BODY and Le DU. Nathalie is a bachelor student coming from Gaume (Belgium) and Le is a post-doc from the P.R. of China.
► Welcome to Alla ISHCHENKO and Esra YILDIZ, both bachelors from the Institut Paul Lambin (Haute Ecole Da Vinci). They will stay with us until end of April 2016.
► Welcome to our new PhD student : Yazhou LIU from the Ghuizou University, Guiyang (P.R. of China).
► Simon Dochain has achieved successfully his PhD thesis entitled "Vers la synthèse totale de l'acide okadaïque".
Short abstract :"Toxin primarily responsible for food poisoning caused by seafood, okadaic acid, a polyether derived from marine dinoflagellates, showed a particularly interesting biochemical tool. Its properties of potent and selective inhibition of protein phosphatases 1 and 2A (PP1 and PP2A) have made one of the most mechanistic probes used for understanding these processes involving enzymes.
In this thesis,he synthesis was based on a cut into three fragments. The Western core fragment was constructed using chemical allyl selenides, which can easily be transformed into allyllithium under the action of n-BuLi. The ISMS methodology then allowed us to assemble a racemic model of lower Central fragment. Finally, two distinct methodologies allowed us to get the East fragment of polyether. The modified conditions Taddei-Ricci, followed by the photochemical oxidation of Suárez, constituted the first route while the electrochemical oxidation of a malonic acid was used as a key step to the second pathway".
► Welcome back Vivian! Vivian Lioret, from the Université de Bourgogne (Dijon, France) is coming back in our lab for a period of 6 weeks. Another french student, Jérémy Caburet from the Université de Franche-Comté (Besancon, France) has also joined the group for the same period of time.
► Welcome to the young chemists Typhaine Lasselin and Nemegaire Maude. They are coming from the High School and they will stay one month in our lab.
► Great! Geraldine Henroteaux succesfully presents her PhD thesis entitled "En Route Towards Novel Jerangolid analogues".
Short abstract : "The continuous growth of fungal infections, coupled with the increased resistance of many microorganisms towards antifungal compounds, is an alarming health problem and the discovery of new antifungal agents has become a particularly important area of research. Jerangolid D is a potential antifungal agent of major interest. Recently, the first total synthesis of this natural product has been reported by our group.
Its structure can be divided into three subunits: a substituted dihydropyran, an unsaturated lactone and a skipped 1,4-diene middle fragment. Our purpose is to operate a series of chemical modifications on these three subunits in order to create a set of new compounds, similar to Jerangolid D, but possessing hopefully enhanced stability, increased activity and lower toxicity.
In this thesis, we shall initially describe our efforts towards the synthesis of the substituted dihydropyran. In order to do so, two methodologies have been developed, based upon previous work in our laboratory. The second one gave the best results and enabled access to the desired dihydropyran in 6 operations using an intramolecular silyl modified Sakurai cyclisation (ISMS) as the key step.
The same pathway was used to construct new dihydropyrans by modifying the C-C triple bond.
With the natural DHP in hand, different modifications were applied to the double bond in order to reach the right-hand fragment of jerangolid B, E and H in which the stereochemistry at C14 was still unknown.
Subsequently, we will describe our efforts towards the preparation of the left-hand lactone of jerangolid D as well as a set of new analogues.
Finally, we will present some preliminary investigations on the synthesis of new analogues of the central part of these natural products."
► Welcome to Arnaud Dykmans bachelor from the Institut Paul Lambin (Haute Ecole Da Vinci). He will stay with us until April 2015.
► Congratulation Akina! Akina Horiuchi successfully presents her PhD thesis entitled "Anionic Polycyclization Towards The Total Synthesis of Indole Alkaloids and Morphine Derivatives".
Short abstract :"Aspidosperma alkaloids receive special attention of synthetic chemists due to their enticing structures and a wide range of remarkable biological activities. A Key feature of these molecules lies in its tetracyclic scaffold, the 6-6-6-5 ABCE ring system called Büchi’s ketone, from which many aspidosperma alkaloids could be elaborated. As part of our ongoing efforts to rapidly access to indole alkaloids, A new sequential polycyclization to the 6-6-6-5 ABCE tetracyclic framework of aspidosperma alkaloids has been developed. Specifically Lewis-acid mediated spirocyclization of a sulfonamide-activated enone, synthesized from tryptamine derivatives, afforded spiroindolenine intermediate; subsequent ring closing imino-aldol reaction afforded a tetracyclic product. We next turned our attention to the total synthesis of a different family of alkaloids, morphine derivatives. Another novel anionic polycyclization to afford the 6-5-6-6 ACNO teteracyclic core of morphine has been developed.
Finally, the synthetic utility of this methodology was demonstrated by the application to the short and efficient synthesis of ACNO analogue of morphine, which is expected to be a potent novel analgesic."
► Welcome to Kim Gosseye, bachelor from the Institut Paul Lambin (Haute Ecole Da Vinci). He will stay with us until January 2015.
► Welcome to the new undergraduate students : Damien Dewez, Julien Masset and Jérôme Savary. They will stay with us in the lab until June 2015!
► Great ! Christophe Eviolitte successfully presented his PhD thesis entitled "Nouvelle application des orthoesters fonctionnalisés : Vers la synthèse d’alcaloïdes".
Short abstract : "Alkaloid Synthesis has always fascinated chemists both by the complexity of the structure of these natural products and by their diversity. To carry out these syntheses, ingenuity and originality were saught after to develop ever more simple, efficient and versatile methodologies. It is therefore in this very challenging context that our research project was born. For many years, our laboratory has been interested in the use of functionalized orthoesters as versatile reagents in order to build complex structures. The main objective of our work is to extend the previously developed annelation methodology by orthoesters to the pyrrole--‐based silyl enol to enter the field of the synthesis of polycyclic alkaloids."
After the completion of this huge work, he will be able now to continue to work on his First Spin-Off project .
July to September 2014
► We finally moved! After 2 long years of work in the A-wing of the Bâtiment Lavoisier in Louvain-la-Neuve, the group of Organic and Medicinal Chemistry of the professor Markó moved from the C-wing to the new restored A-wing. It took time to move everything and sometimes it was tedious but we did it. We are now in the new laboratories; the environment is clear and the security is at the top level. It's time to work now...
► The 18th edition of the Ph.D. Students' Day, organised by the Institute of Condensed Matter and Nanosciences, was held on Friday the 23rd of May. During this one-day meeting, young researchers are invited to give oral lectures and present their work during a poster session. One of our PhD students, Simon Dochain, won the price for the best poster. Congratulations Simon.
► Laura Marchand joined the group on mid-april. She's coming from France, Université de Franche-Comté (Group of professor Fabrice Lallemand).
► Well done! Gheorghe Catrinescu presented successfully his PhD thesis entitled "Novel diastereoselective allylations as key-steps in the total synthesis of natural products".
Short abstract :"In this thesis, we synthesized polyhydroxylated fragments; these fragments are present in natural products possessing interesting biological properties. Two main patterns can be distinguished: skipped and contiguous polyols. Regarding contiguous polyols, it was decided, at the onset of this work, to investigate possible pathways to access, at will, all four possible diastereoisomers of a 1,2,3-triol. The likelihood of obtaining amino diols was also envisioned.
Therefore we examined the addition of achiral allylstannanes (type II or III) to functionalized chiral aldehydes (α-benzyloxy or α-dibenzyl amino aldehydes). This approach led to the synthesis of anti-syn (type II allylstannane) and syn-anti (type III allylstannane) triols as well as syn-syn amino diols (type II allylstannane) with good diastereoselectivities. This efficient new tool (establishing two new stereocenters in one operation) was then employed in the total synthesis of natural bioactive products. The first target was ( ) cleistenolide and its synthesis was accomplished in 12 linear steps starting from cheap D-mannitol. The formal total synthesis of a second natural compound, herbarumin I, was achieved and required 9 linear steps starting from 1-pentene.
The above mentioned tool was used in the synthesis of 2,6-trans-tetrahydropyrans, a part of our synthetic endeavour towards the total synthesis of amphidinol 3 (a potent haemolytic and antifungal natural product). Our efforts in their preparation and subsequent functionalization complete this thesis".
► Welcome to a series of young "chemist" coming from High schools : William's Fritsch (Institut Saint Vincent de Paul, Belgium), Alexandre Grossiels (Collège Saint Jean), Abdhelhak Stitou (Institut de la Sainte Famille, Belgium) and Laurent Serra (Institut Lambion, Belgium). They will stay with us for a period varying from 3 to 4 weeks.
► Welcome to Laurent Scheepers, bachelor from the Institut Paul Lambin (Haute Ecole Da Vinci). He will stay with us until April 2014.
► Welcome to the new postdoc, Yohan Macé. Yohan joined our group, after spending 2 years in the professor Riant's group (UCL). During this period he worked on a confidential medicinal chemistry project, focused on the development of new anti-angiogenic molecules selected for their efficacy in hypoxic conditions. He has performed his studies in France where he became Doctor in the Institut Lavoisier de Versailles, Université de Versailles (France) under the supervision of Dr. Blazejewski and Magnier. His PhD thesis was entitled : "Synthesis and reactivity studies of new electrophilic perfluoroalkylkating reagents. Electrophilic". Yohan will stay with us for a period of 6 months.
► Great ! Steve Dierick presented successfully his PhD thesis entitled "New N-Heterocyclic Carbene Complexes for Catalytic Hydrosilylation and Organometallic Chemistry".
Short abstract :"In this thesis, a new generation of N-heterocyclic carbene platinum catalysts has been developed for the hydrosilylation of alkenes, alkynes and allenes. These complexes possess high activities and display exquisite stereoselectivities whilst being efficient at low catalyst loadings. They tolerate a wide range of functional groups and the precatalyst precursor is readily available, insensitive towards air and moisture, bench-stable for extended periods of time and easy to handle. These qualities make them the ideal user-friendly catalysts for hydrosilylation. In general, all the reagents are mixed directly from their bottles and stirred in air without any precaution. Furthermore, the use of solventless conditions, coupled with a fully atom-economical transformation, leads to a true green process, attractive for industry. Additionally, an exceptionally bulky N-heterocyclic carbene has been designed, fully characterized and engaged in the formation of several organometallic complexes. IPr*(2‑Np) appears to be the most sterically demanding NHC reported to date. It is noteworthy that its ability to modify its overall shape enables IPr*(2‑Np) to accommodate various coordination environments whilst still remaining one of the most σ-donating NHCs".
Steve will now join the group of professor Jef De Brabander in the Texas University (Dallas, Texas).
► Welcome to Kenji Kopf, bachelor from the Institut Paul Lambin (Haute Ecole Da Vinci). He will stay with us until january 2014.
► Welcome to the new undergraduate students : Nadzeya Kryvutsa, Nicolas Diercxsens, Laurent Gillard and Jean-Boris Nshimyuremyi. They will stay with us in the lab until July 2014!
► Great ! Florian Schevenels presented successfully his PhD thesis entitled "A new reaction in heterocyclic chemistry".
Short abstratc : "In this thesis, he started with a perilous total synthesis of a triterpene: spiroiridal. An unexpected reaction occurred during this synthetic quest and became of major interest. He discovered, studied, extended and applied a new reaction in heterocyclic chemistry. Mixing a base, 1,1- dichloroethylene and an appropriate ketone (or aldehyde), led to the efficient preparation of (Z)-chloromethylene-ketals, benzofurans, benzothiophenes, indoles, N-sulphonylindoles, (Z)-chloromethylenetetrahydro-furans, -thiophenes and -pyrroles. This new and powerful tool in organic chemistry was used to synthesise small or complex bioactive products, culminating in a 19-step synthesis of an RXR inhibitor and two patents securing the preparation of new kinase inhibitors".
He will now join the group of professor Scott Snyder in the Scripps Research Institute (Jupiter, Florida).
► Congratulations : Three of our undergraduate students ended their studies with the title of Master in Chemistry. Jean-François Body presented his undergraduate thesis entitled "Vers de nouveaux analogues du Jérangolide D"; he will start a PhD in our lab in the beginning of September.
Marion Peeters presented her thesis entitled "Vers la synthèse du fragment central de l'acide OkadaÏque"; Thibaut Debande presented his thesis entitled "Vers l'insertion de cyclopropanes par couplage-croisé de Hiyama".
► Kangsa Amporndanai (our Thai bachelor arrived in June) went back to the University of Maidol in Thailand, after spending more than two months, of hard work, in our lab. Now he is headed back to Maidol University to achieve his master thesis. Good luck Kangsa.
► Welcome back! Dr François Chellé joined the laboratory for a period of 8 months. François is a former post-doc student of the lab; he left the lab in 1996. He will be interested in the preparation of platinum-carbene catalysts. Good work François.
► Congratulations to Simon Dochain (PhD Student) : he was awarded of the title of best oral presentation during the PhD Day, held in Louvain-la-Neuve on May 24th. This award is the 2nd in two years for our lab! Well done.
► Professor Markó et al. published a book entitle "Climat : 15 vérités qui dérangent" (Ed. Texquis - ISBN : 978-2-930650-05-0). The other authors are : A. Debeil, L. Delory, S. Furfari, D. Godefridi, H. Masson, L. Myren and A. Préat.
► April 19th : "20 Years of Organic Chemistry and Beyond". This one-day meeting was a great moment. Nearly 90 alumni gathered to celebrate the 20th Anniversary of the Laboratory of Professor Markó. Former students issued from industry or academy, presented oral lectures. They were coming from Belgium, Switzerland, Germany, France, United Kingdom, USA, Thailand...Professor Markó was pleased to meet all the former student and great surprise, the first PhD of the lab joined us!
► Professor Markó is pleased to announce that Dr.Mannepalli Lakshmi Kantam (first postdoc student of Professor Markó) has been appointed as Director of Indian Institute of Chemical Technology, Hyderabad by Government of India.
► Welcome to a new student coming from France. Vivian Lioret is coming from the "Institut Universitaire de Technologie" (IUT) de Besançon-Vesoul. He will stay in the lab for 14 weeks.
► Dear Hodney. 15 February, you finished your 2-years postdoc in our laboratory. We all remember your extremely pleasant character and your passion for big cities : Paris (of course!) and Brussels. Louvain-la-Neuve was not big enough for you! You are now moving to the University of Antwerp, in the Prof. B. Maes group, Department of Chemistry, Organic Synthesis. We all wish you the best for your scientific career, Dr Hodney Lubin.
► One of our former students, Dr De Bo Guillaume, was awarded a scholarship from Wallonia-Brussels International in 2011-2012 to perform a 12 months postdoctoral stay at the University of Edinburgh and most recently at the University of Manchester (UK). An article published online on January 11, 2013 in "Science Magazine" reports a breakthrough: a molecular machine created by these chemists captures and assembles amino acids in the correct order to make protein sequences. Well done Guillaume!
► One of our former students, Dr Nuno Maulide (Max Planck Institut für Kohlenforschung in Mülheim), became the award winner of the Bayer Early Excellence in Science Award 2012. The scientific jury has accomplished the selection procedure from a list of eminent candidates. Nuno recivied this prize for developping new routes to highly functional small synthetic molecules (more information on the Maulide group).
► After two years of fruitful collaboration, postdoc Huoming (Dr Li) went back to China. Huoming was highly appreciated by all members of the laboratory and its departure makes us sad. We wish him full success in his continuing scientific career. Best wishes Huoming!
► Time flies quickly!
25 years ago, a small group of courageous students started a new lab at the University of Sheffield, UK.
20 years ago, this group moved to the Université catholique de Louvain of Louvain-la-Neuve, Belgium.
To celebrate this unique event, a one-day symposium, with lectures by Alumni of the group, will be held on April 19th,2013.
► Welcome to 2 new colleagues coming from China. Dr Xaio-Feng Ma from Chengdu Institute of Biology, Chinese Academy of Sciences (Ph.D. in Medicinal chemistry) will start a posdoc in our laboratory and Xi-Ya Luo, a new PhD student, comes from Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences.
► Great ! Gulluzar Bastug presented successfully his PhD thesis entitled "Préparation de bicycles fonctionnalisés : vers la synthèse totale de la (+)-pestalotiopsine A et de la lactone du vin".
Short abstract :"In this thesis, she developed the use of functionalized orthoesters as annelation agents for the preparation of aromatic bicycles of benzothiazole, benzoxazole and benzimidazole type. Furthermore, different strategies for the synthesis of γ-butyrolactones fused to a cyclobutane or cyclohexane have also been explored to synthesize (+)-A pestalotiopsine and wine lactone. These approaches are based on condensation reactions of orthoesters followed by radical cyclizations or allylations reactions catalyzed by chromium or indium".
She will now join (as a postdoc) the group of Professor Steven Nolan in the University of St Andrews (UK).
► Great ! Alécia Vandenberghe presented successfully his PhD thesis entitled "Botanochimie: Utilisation de matériel végétal comme alternative originale pour la résolution cinétique du 1-phényléthyl acétate". Her thesis was characterized by constant movement into different laboratories she needed to perform her work. For instance she was in the professor Markó lab for organic synthesis, botanochemistry test and gas chromatography analysis , in the Centre de Recherche Public Gabriel Lippman (Luxembourg) for protein purification...
► Welcome to the three news PhD students : Alice Ameryckx, Pol Karier and Thomas Xhurdebise. Both performed their master thesis in our group.
► Great ! Professor István Markó is extremely proud to announce that the first generation catalyst developped in our laboratory is now commercialized by UMICORE. This advanced Platinum N-heterocyclic carbene catalysts expanded the range of hydrosilylation applications for both silicone and fine chemical industries. This new type of catalyst offers advantages over conventional types of hydrosilylation catalysts in terms of selectivity, activity and productivity. Due to the stabilizing effect of the strongly binding N-heterocyclic carbene ligand, formation of platinum colloids is avoided and formation of byproducts via isomerization or hydrogenation is suppressed.
► After four years of collaboration, Dr Jiri Pospisil will leave the laboratory of Medicinal and Organic Chemistry (Professor I.E.Markó) and will join the group of professor Samir Zard in Paris (Ecole polytechnique). We wish him full succes in his new position.
► Welcome to the new three new undergraduate students : Marion Peeters, Jean-François Body and Thibaut Debande.
► Professor I.E.Markó is proud to announce that previous work done by our group was recognised for its quality!
A modified version of Markó’s aerobic oxidation procedure, using highly pure CuCl with 4,7- diphenyl-1,10-phenanthroline, DBAD, and Cs2CO3 successfully oxidized primary and secondary alcohols to the corresponding aldehydes and ketones in excellent yield at room temperature with either air or molecular oxygen under atmospheric pressure. This work was performed by the group of Professor Tetsuto Tsunoda, at the Faculty of Pharmaceutical Sciences of Tokushima (Japan) (Tetrahedron Letters, 2012, 53, 5880-5882). Congratulations to professor Tetsuto Tsunoda for his splendid contribution.
► Great : Freddi Philippart presented successfully his PhD thesis entitled "Vers la synthèse totale du Polycavernoside A". He is currently working in the group of professor Jun Okuda in the Institute of Inorganic Chemistry - RWTH Aachen University (Germany).
► Congratulations : Six of our undergraduate students ended their studies with the title of Master in Chemistry. Alice Ameryckx presented her undergraduate thesis entitled "Electrolyse de malonates. Vers la synthèse de spirocétals"; Thomas Xhurdebise presented his thesis entitled "Triquinanes Angulaires via les Orthoesters Insaturés. Vers la Synthèse Totale du Pentalénène". Both will start a PhD in our lab in september; they will join Pol Karier, who already presented his master thesis in June.
Sophie Moreau presented her thesis entitled "Vers de nouveaux analogues du Jerangolide D", Emilie Vercruysse presented her thesis entitled "Hydrosilylation d'alcènes catalysée par des complexes NHC-Platine (0)", Jemina Deldicque presented her thesis "Vers la synthèse de la lactone du vin" and finally Philippe Steinbusch presented his thesis entitled "Towards the synthesis of pedicularis lactone".
► Two new publications for the laboratory, one by Alécia (botanochemistry) and the other one by Quentin.
"Enantioselective hydrolysis of racemic 1-phenylethyl acetate by an enzymatic system from fresh vegetables", Alécia Vandenberghe, István E. Markó, Fabio Lucaccioni, Stanley Lutts, Industrial Crops and Products 42 (2013) 380– 385
Abstract : High valuable enantiomerically pure compounds are potential chiral building blocks for the synthesis of pharmaceutically important molecules, agrochemicals, flavors and asymmetric chiral ligands. A novel methodology coined “botanochemistry” investigates the possibility of using directly freshly cut pieces of various vegetables, without any other processing to perform important chemical transformations. The present work aims to optimize the time required for the preparation of the biocatalysts and to screen among fruit and vegetable organs for this purpose. It was observed that most of those biocatalysts contain specific enzymes that hydrolyze exogenous organic substrates. The red beetroot skin has been selected as the most promising biocatalyst to perform the kinetic resolution of (±)-1-phenylethyl acetate with excellent enantiomeric excess. The main advantage of this approach, as compared to the chemical procedures (metal- and organo-catalysis), is that the final consequences of these transformations are more ecologically friendly, economically promising and also enables the valorization of by-products issued from agriculture and food industries.
"Interaction network of antimicrobial peptides of Arabidopsis thaliana, based on high-throughput yeast two-hybrid screening", Coralie Damon , Julia Dmitrieva, Yordan Muhovski, Frédéric Francis, Laurence Lins, Quentin Ledoux, William Luwaert, István E. Markó, Sergio Mauro, Marc Ongena, Philippe Thonart, Pascal Veys, Daniel Portetelle, Jean-Claude Twizere, Micheline Vandenbol, Plant Physiology and Biochemistry 58 (2012) 245-252
Abstract : One mechanism used by plants to respond to infection is the production of antimicrobial peptides (AMPs). In addition to a role in defence, AMPs seem to have other biological functions. Furthermore, the number of cysteine-rich AMP-like peptides appears to have been underpredicted in plant genomes. Such peptides could be involved in plant defence and/or in other biological processes. Here we generated an interaction network between 15 AMPs/AMP-like peptides and ca. 8000 other Arabidopsis thaliana proteins (AtORFeome2.0) and found 53 putative novel interactions. These interactions involve five transcription factors, a subunit of the COP9 signalosome, a heat shock protein, a MAP kinase kinase, a thioredoxin and 4 uncharacterized proteins.
► First publication issued from the cooperation between the Dalian University of Technology and professor I.E.Markó.
"Evidence of Two Key Intermediates Contributing to the Selectivity of P450-Biomimetic Oxidation of Sulfides to Sulfoxides and SUlfones", Xinrui Zhou, Xian Chen, Yaqin Jin, István E. Markó
Chemistry, An Asian Journal, DOI: 10.1002/asia.201200422.
Abstract : A mild process for the selective oxidation of sulfides is in great demand. Therefore, probing the mechanism underlying the biological oxidation of sulfides under ambient conditions may provide valuable insights for the development of such a reaction. Based on porphyrin models of P450 enzymes, evidence of two key intermediates, Int0 and Int1, in this reaction is provided. Spectroscopic studies indicated the formation of a hydroperoxide-iron(III) species (Int0) upon addition of H2O2 . This intermediate proved to be highly selective for sulfoxide production. By contrast, a defined porphyrin oxoiron(IV) cation radical (Int1) directly reacted with sulfoxides, leading selectively to the corresponding sulfones. Interestingly, the available sulfoxides reversibly act as a new axial ligand for Int0 forming a more active species Int0(SO) . The amount of Int0 increased in the presence of alkyl, aryl, or aromatic sulfides, while Int1 formed in the absence of these sulfides. Thus, sulfoxides and sulfones would selectively form under conditions that favor the corresponding intermediates, which elucidate the biological oxidation pathway.
► On July 17th, Professor István E. Markó gave a lecture on the Belgian Organic Synthesis Symposium (BOSS XIII, Leuven, Belgium). The lecture was entitled :"Total Synthesis of Complex Natural Products : An Exercise in Serendipity".
► István Markó, Seasky Research Distinguished Visiting Professor.
On July 9th, István Markó, professor at the Institute of Condensed Matter and Nanotechnology (IMCN), has been elected Seasky Research Distinguished Visiting Professor at the prestigious Dalian University of Technology , Dalian, China, for 2012-2014.
The State Key Laboratory of Fine Chemicals (SKLFC) from Dalian University of Technology, Dalian, China, awarded every year a foreign researcher for outstanding contributions in the field of chemistry.
Organic chemistry, organic synthesis and organometallic catalysis were selected for the award of the prize. In this context, Professor István Markó spend four weeks a year for three years on the new campus of Dalian University of Technology, Dalian, to give courses and lectures, discuss research and create meaningful interactions with students and the Chinese professors.
It is also expected in Singapore and other Chinese universities.
► On July 5th, Professor István E. Markó gave a lecture in the Dalian University of Technology (China). The lecture was entitled :"Organic chemistry is the Chemistry of Life. Organic Chemistry is Life" .
► Congratulations : after the presentation of his undergraduate thesis entitled "Synthèse Totale du (-)-Cléisténolide", Pol Karier ended its studies with the title of Master in Chemistry. He will start a PhD in our lab on september.
► Congratulations! Akina Horiuchi (PhD student) has been selected to accompany Her Royal Highness, the Princess of Belgium, our chancelor and a team of industrial and academic people to foster new relationship with japanese universities. (9 to 16 of June 2012).
► Congratulations to Steve Dierick (PhD Student) : he was awarded of the title of best oral presentation during the PhD Day, held in Louvain-la-Neuve on 1st June.
► Movie made in the lab by Lab'InSight.
► Presentation of the Lab'InSigh video and the main research areas of the lab at the special day organized in FUNDP, Namur (25th May 2012) : "Bioproducts : from the molecules to materials". After a 5 minutes presentation of the lab by Christophe Eviolitte (PhD Student), Christophe and Fabio Lucaccioni (Head Chief Technician) answered to the questions of industry people.
► A method for reducing a ketone or ester in the presence of an aldehyde bypasses the standard carbonyl reactivity hierarchy, is reported in the paper "Highly Chemoselective Reduction of Carbonyl Group in Presence of Aldehyde", Gulluzar Bastug, Steve Dierick, Frédéric Lebreux, and István E. Markó, Org. Lett., 2012, 14 (5), pp 1306–1309. It is also reported by the RSC Chemistry World online journal : "Bending carbonyl reactivity rules".
Abstract : The exquisite ability of diethylaluminum benzenethiolate to efficiently discriminate between aldehydes and other carbonyl functions enables the chemoselective in situ reduction of ketones and methyl esters in the presence of aldehydes. This potent strategy avoids the usual drawbacks of traditional protecting group methodologies and could be extended to various other transformations.
► "Efficient and Connective Assembly of Highly Functionalized Benzofurans Using o-Hydroxyphenones and Dicxhloroethylene", Florian Schevenels and István E. Markó, Org. Lett., 2012, 14 (5), pp 1298–1301.
Abstract :The preparation of highly functionalized benzofurans by a unique and connective transformation is reported. Base-catalyzed condensation of o-hydroxyphenones with 1,1-dichloroethylene generates the corresponding chloromethylene furans. These labile intermediates undergo a facile rearrangement into benzofuran carbaldehydes under mild acidic conditions.