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OP-29 ISBOMC `10 5.7 – 9.7. 2010 Ruhr-Universität Bochum Peptide-carbenes and peptide-phosphines transition metal catalysts for “Green” solid phase catalysts. Morten Meldal, *a Kasper Worm-Leonhard, a and Christian A. Christensen a a Carlsberg Laboratory, SPOCC-Centre, Gamle Carlsberg Vej 10, 2500 Valby, Denmark, E-mail: mpm@crc.dk In Nature metalloproteins play a crucial role in complex biochemical transformations while displaying exquisite regio- and enantio-selectivity. More importantly the protein framework coordinates the catalytic metal and ensure substrate match and lower activation energy of the reaction to provide very high turnovers, which in turn facilitates the efficient biochemical transformation at low concentration of the catalytic protein. These properties can advantageously be mimicked in the field peptide and peptide-organic chemistry to putatively create catalysts for “green” chemistry. By engineering the peptide scaffold with one or several ideal ligands for a variety of transition metals, e. g. Pd, Zn or Cu. artificial enzyme like compounds, displaying selectivity and turnover for general organic chemistry transformations may be obtained. This presentation describes the synthesis and application of carbene- and phosphine-precursors for incorporation into peptide frameworks that folds around a transition metal and forms relatively compact and stable globular structures with an enzyme like binding cavity for substrate binding and catalysis. The strategy is modular and well suited for a Split/Mix approach where a large number of catalysts may be generated in a single combinatorial synthesis. Backbone phosphinylated peptides (1) were synthesized on polar PEGA supports and in solution and the catalytic activity was compared. The solid supported catalysts were very efficient and could be recycled at least 5 times without loss of activity. The palladium coordination of the phosphine could furthermore be combined with folding and complexation with other dedicated functional groups in the peptide. Backbone carbenes (2) formed extremely stable palladium-peptido carbene complexes that did not loose any activity with time or use. These solid phase catalysts could be used in microwave assisted C- C and C-N couplings in water with good selectivities and quantitative yields. References 1. (a) C. A. Christensen and M. Meldal. Efficient Solid-Phase Synthesis of Peptide Based Phosphine Ligands: Towards Combinatorial Libraries of Selective Transition Metal Catalysts. Chem. Eur. J. 2004, 11, 4121-4131; (b) C. A. Christensen and M. Meldal. Solid-phase synthesis of a P,S-ligand system designed for generation of combinatorial peptide-based catalyst libraries. J. Comb. Chem. 2007, 9, 79-85. 2. (a) J. F. Jensen, K. Worm-Leonhard, and M. Meldal. Optically active (peptido-carbene) palladium complexes: towards true combinatorial solid phase libraries of transition metal catalysts. Eur. J. Org. Chem. 2008, 3785-3797 (b) K. Worm-Leonhard and M. Meldal. Green catalysts: Solid-phase peptide carbene ligands in aqueous transition metal catalysis. Eur. J. Org. Chem. 2008, 5244-5253. 45
OP-30 ISBOMC `10 5.7 – 9.7. 2010 Ruhr-Universität Bochum Construction of an Immunosensor via Copper-Free ‘Click’ Reaction Between Azido SAMs and Alkynyl Fischer Carbene Complex. Application to the detection of Staphyloccal Enterotoxin A Pratima Srivastava, a Amitabha Sarkar, b Sudeshna Sawoo, b Amarnath Chakraborty, b Pinak Dutta, b Othman Bouloussa, c Claire-Marie Pradier; d Souhir Boujday, d and Michelle Salmain *a a Ecole Nationale Supérieure de Chimie de Paris, Laboratoire Charles Friedel (UMR CNRS 7223), 11, rue Pierre et Marie Curie, 75231 Paris cedex 05, France. b Indian Association for the Cultivation of Sciences, Department of Organic Chemistry, 700032, Kolkata, India. c Institut Curie, laboratoire Physico-chimie Curie (UMR CNRS 168), 26 rue d’Ulm, 75248, Paris , cedex 05, France. d Université Pierre et Marie Curie, Laboratoire de réactivité de surface (UMR CNRS 7197), 4 place Jussieu, 75252, Paris cedex 05, France. E-mail: pratima-srivastava@chimie-paristech.fr Keywords: Immunosensor, IRRAS, ‘click’ reaction, Fischer carbene, antibody-antigen reaction. A copper-free « click » reaction between azido-terminated self-assembled monolayers (SAMs) on gold and an alkynyl Fischer carbene complex yielded functionalized surfaces on which facile and swift grafting of amine-containing molecules was achieved via aminolysis of the Fischer carbene moieties (Figure). 1 S + N3 N N N MeO W(CO) 5 Ph NH2 Au Au S Au S OMe W(CO) 5 46 (OC) 5W This 3-step process could be conveniently monitored by Infrared Reflection-Absorption Spectroscopy (IRRAS). An extensive study of the different parameters involved in the covalent grafting of proteins on the Fischer carbene modified SAMs was carried out. As an application, an antibody against Staphylococcal Enterotoxin A (SEA) was immobilized onto gold chips so as to ultimately construct an optical immunosensor for the detection of this toxin in food samples. References 1. S. Sawoo, P. Dutta, A. Chakraborty, R. Mukhopadhyay, O. Bouloussa, A. Sarkar, Chem. Commun. 2008, 5957-5959. NH N N N Ph
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Sergey Abramkin Universität Wien,
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Tensim Dallagi ENSCP, France t.dall
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Prof. Dr. Toshikazu Hirao Osaka Uni
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Obiora Augustine Orakwue Hyqid Nige
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Book of Abstracts - Ruhr-Universität Bochum

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