ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
2017 Workshop « Electron Transfer, Radical Ions and Radical Chemistry ». March 23 and 24, 2017. Université Lyon 1 Campus LyonTech – La Doua
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
On behalf of the organizing committee, I warmly welcome you to this first Workshop edition that will focus on electron-transfer reactions and reactivity of radical ions and radicals. The program spans a range of topics of radical and electron-transfer processes in organic chemistry, electrochemistry, radical and electron-transfer induced polymerization processes, photo-electrochemistry, photoredox catalysis, catalysis and theory. This event will honor Professor John A. Murphy (University of Strathclyde, Glasgow, Scotland) who is an invited Professor at the Université Claude Bernard Lyon 1 from March 22 to April 20, 2017. I would like to express my sincere thanks to all members of the organizing committee for their continuous and enthusiastic efforts. The cellule financière of the ICBMS is also acknowledged for their help. I am also grateful to our generous institutional and industrial sponsors, who have made this event possible. I wish you all a very fruitful workshop and a pleasant stay in Lyon. Maurice MEDEBIELLE
Organizing committee: Maurice Médebielle, Lionel Perrin, Paolo Larini and Anis Tlili. Université Claude Bernard Lyon 1, ICBMS UMR 5246.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
GENERAL INFORMATION
Location
The workshop will take place at the CPE Lyon – Ecole Supérieure de Chimie Physique Electronique de Lyon
Locate CPE building and Tramway stations LA DOUA GASTON BERGER and UNIVERSITE LYON 1:
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
To access the Université Claude Bernard Lyon 1 campus (La Doua) and location of the Workshop, please use tramway lines T1 (bound to IUT Feyssine) or T4 (bound to La Doua-Gaston Berger, Terminus) and get off at La Doua – Gaston Berger’s station. Both lines are connected to Part Dieu Railway Station (20-22 minutes).
From Lyon Saint-Exupéry Airport, you can reach Part Dieu Railway Station using the Rhône- Express Train: https://www.rhonexpress.fr/en
Transport
Local public transport: http://www.tcl.fr
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Internet
Wifi access will be provided during the Workshop
Working language
The working language of the workshop is English
SPONSORS
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
SCIENTIFIC PROGRAMME
DAY 1 Thursday March 23 DAY 2 Friday March 24
8:30-9:10 Registration 8:30-8:55 Registration 9:15-9:30 Welcome 9:00-9:25 T. NOEL 9:30-10:00 J. A. MURPHY 9:30-9:55 B. KONIG 10:00-10:15 10:00-10:25 M. BRASHOLZ 10:20-10:45 S. ZARD 10:30-10:45 Break 10:50-11:15 Y. LANDAIS 10:50-11:15 M. E. BUDEN 11:20-11:45 L. FERAY 11:20-11:45 A. TLILI 11:50-12:15 C. OLLIVIER 11:50-12:15 M. PUIATTI 12:30-14:00 Lunch 12:30-14:00 Lunch 14:15-14:40 J. BROGGI 14:15-14:40 F. MASERAS 14:45-15:10 D. GIGMES 14:45-15:10 V. ROBERT 15:15-15:40 E. LACOTE 15:15-15:40 L. PERRIN 15:45-16:10 Break 15:45-16:10 Break 16:15-16:40 J. BONIN 16:15-16:45 Feedback 16:45-17:10 N. LE POUL 16:45-17:00 Farewell 17:15-17:40 C. BUCHER 17:45-18:10 M.-N. COLLOMB
19:45 Dîner
Speakers
PLENARY LECTURE
John A. MURPHY (Glasgow, Scotland): Evolution of Organic Super Electron Donors
INVITED LECTURES
Samir ZARD (Ecole Polytechnique, Palaiseau): Radical-Polar Crossover: Manifold Implications for Synthesis
Yannick LANDAIS (Université de Bordeaux, Bordeaux): Free-Radical Additions to Olefins. Recent Developments and Applications
Laurence FERAY (Université d'Aix-Marseille, Marseille): α-Bromoacrylate as radical acceptor in dialkylzincs-mediated radical-polar crossover processes, theoretical investigation and synthetic applications
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Cyril OLLIVIER (Université Pierre et Marie Curie, Paris): Photoredox Catalysis for the Generation of Carbon Centered Radicals and Synthetic Applications
Julie BROGGI (Université d’Aix-Marseille, Marseille): New horizons for Organic Electron Donors
Didier GIGMES (Université d’Aix-Marseille, Marseille): Photopolymerization initiators: Synthesis and photochemical studies
Emmanuel LACOTE (Université Lyon 1, Villeurbanne): Organic and Polymer Free-radical Synthesis using NHC–Boranes
Julien BONIN (Université Paris Diderot, Paris): Molecular Catalysis of the Photochemical Reduction of CO2 into CO and beyond: on the Road to Solar Fuels
Nicolas Le POUL (Université de Brest, Brest): Surface functionalization by model complexes of copper enzymes: the “self-induced electroclick” approach
Christophe BUCHER (ENS Lyon, Lyon): Electron-triggered metamorphism in viologen-based (supra)molecular materials
Marie-Noëlle COLLOMB (Université Grenoble Alpes, Grenoble): Photo-induced redox catalysis for hydrogen production with molecular compounds
Timothy NOEL (TU Eindhoven, Pays-Bas): Engineering of photocatalytic reactions in microreactors
Burkhard KONIG (Université de Regensburg, Allemagne): Visible light photoredox catalysis with radical anions
Malte BRASHOLZ (Université d'Hambourg, Allemagne): New photoredox-induced cascade reactions
Maria Eugenia BUDEN (Université Nationale de Cordoba, Argentine): Photoinduced Electron Transfer in base-promoted Homolytic Aromatic Substitution and Related Systems. Is t-butoxide anion a key ingredient?
Anis TLILI (Université Lyon 1, Villeurbanne): KOtBu promoted intermolecular cross-coupling through electron transfer
Marcelo PUIATTI (Université Nationale de Cordoba, Argentine): “The Palme d'Or goes to ...". A search for the best functional for dealing with anionic organic species
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Feliu MASERAS (Tarragone, ICIQ, Catalogne): Characterization of single electron steps in water oxidation through DFT calculations
Vincent ROBERT (Université de Strasbourg, Strasbourg): Charge Transfer Processes: Prime Role of Optimized Molecular Orbitals
Lionel PERRIN (Université Lyon 1, Villeurbanne): Exploring the reactivity of the Kagan’s reagent from a theoretical perspective
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Evolution of Organic Super Electron Donors
J. A. Murphy
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, United Kingdom * [email protected]
My research group has been fortunate to develop a number of simple organic electron donors, structurally related to enols, enolates and enamines; in this way, we have built upon the excellent pioneering work of many people including Bunnett,1 Rossi2 and Narasaka.3 Our starting point was to ask whether a neutral organic ground state molecule could reduce an aryl halide. The search for such a molecule led us to understand some of the factors that control the power and selectivity of organic electron donors, and their scope as reducing agents.
1,00E-05
5,00E-06
0,00E+00 -2,5 -2 -1,5 -1 -0,5 0 -5,00E-06
-1,00E-05 Current/ A Potential/ V -1,50E-05
Being coloured reagents, they readily absorb visible and near-UV light; this adds to their power as donors, and allows them to tackle even more challenging synthetic tasks. This presentation will give an overview of developments relating to these electron donors from our current perspective.
References 1. Scamehorn, R. G.; Bunnett, J. F. J. Org. Chem. 1977, 42, 14491457. 2. Guastavino, J. V.; Rossi, R. A. J. Org. Chem. 2012, 77, 460472. 3. Narasaka, K. Pure & Appl. Chem. 1997, 69, 601604. 9
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Professor JOHN A. MURPHY B.A. (Mod.), Ph.D., C. Chem., F.R.S.C., F.R.S.E. CURRICULUM VITAE http://www.johnmurphygroup.com/
1. Name: John Anthony Murphy Nationality: Irish
2. University Education: 1972-1976 University of Dublin. Awarded B.A. (Moderatorship) First Class. Awards Held: Department of Education Scholar (1972-1976). University of Dublin Foundation Scholar (1974-1979). Goulding Scholar (1975); Gold Medallist of the University (1976); Cocker Medallist for Experimental Chemistry (1976). 1976-1979 University of Cambridge. (Hutchinson Research Studentship.) Awarded Ph.D. in Organic Chemistry (with Prof. Jim Staunton)
3. Appointments Held: 2013-2016 Head of Department 2007-2012 Director, Glasgow Centre for Physical Organic Chemistry 2010- to date Head of Organic Chemistry 2007-2013 Deputy Head of Department 2006-2008 Director, WestCHEM 2004-2006 Deputy Director, WestCHEM 1995- to date Merck-Pauson Professor, University of Strathclyde. 1994-1995 Reader, University of Nottingham. 1983-1994 Lecturer, University of Nottingham. 1982-1983 College Lecturer, Jesus College, Oxford. . 1980-1983 Departmental Demonstrator, University of Oxford. with Prof. J. E. Baldwin on bioorganic chemistry. 1979-1980 Izaak Walton Killam Fellowship, University of Alberta
4. International and National Recognition: 2017 Visiting Professor, Université Claude Bernard (Lyon- 1) 2016 The Charles Rees Award for Heterocyclic Chemistry (Royal Society of Chemistry) 2013 Visiting Lectureship, University of Kyoto 2012 The Bader Award in Organic Chemistry (Royal Society of Chemistry) 2007 Visiting Fellow at the Australian National University. 2004 Visiting Professor, Université Pierre et Marie Curie, Paris
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
2002 D.Sc. (University of Strathclyde) 2001 Presidential Visiting Professor, N.A.I.S.T., Japan. 2001 Elected Fellow of the Royal Society of Edinburgh 2001 Royal Society Leverhulme Senior Research Fellow 1999 Invited “Troisième Cycle” Lecturer, Switzerland. 1998 Elected Fellow of the Royal Society of Chemistry. 1996 Visiting Professor at l’Université d’Aix Marseille. 1995 Visiting Fellow at the Australian National University.
I am an organic chemist and my research group revels in exploring chemical reactivity in synthesis and in biology. My research group website is http://www.johnmurphygroup.com/ We have a particular interest in electron transfer reactions and in radical chemistry, but are generally interested in mechanisms of organic reactions.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Radical-Polar Crossover: Manifold Implications for Synthesis
S. Z. Zard
Laboratoire de Synthèse Organique, Ecole Polytechnique, 91128 Palaiseau, France. [email protected]
Abstract. Our research group is mostly concerned with the discovery and development of new reactions and processes that could be useful in organic synthesis. As is usually the case in scientific research, the interplay between conjecture and chance observation underlies much of our work. Unexpected events often bring a fresh lighting to the system being examined and open doors hitherto unsuspected. Misconception has thus played an important role by allowing us to uncover a number of new radical and non-radical reactions of some generality involving sulfur compounds, acetylenes, oximes, and related derivatives: we simply followed the logical consequences of our observations and went where the chemistry took us. In this lecture, the crossover from the radical to the cationic manifold that can take place in some of these reactions will be presented and the various mechanistic and synthetic implications discussed briefly.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Samir Z. Zard
Personal: Date and place of birth: 18th June 1955, Ife (Nigeria) Nationality: French Marital status: Married, two children Professional Address: Laboratoire de Synthèse Organique, Ecole Polytechnique, 91128 Palaiseau, France. Phone: +33-1-69 33 59 71; Fax: +33-1-69 33 59 72; e-mail: [email protected]
Education: 1978 BSc : Imperial College of Science and Technology, London University (1st Class Honours). ARCS (Associate of the Royal College of Science) 1st Class Honours. Awards: Hofmann Prize; Edward Frankland Prize; Edmund White Prize 1983 PhD : Université Paris-Sud, Orsay, France (supervisor: Professor Sir Derek Barton).
Employment:
CNRS: 1981, Attaché de Recherche; 1983, Chargé de Recherche; 1989, Directeur de Recherche (2nd Class); 1996, Directeur de Recherche (1st Class); 2003, Directeur de Recherche (Exceptional Class). Ecole Polytechnique: 1986, Maître de Conférences (part- time); 2000, Full Professor (part-time).
Field of research: Discovery and mechanistic study of new reactions and processes. Publications: 342; Patents: 37
Honors and distinctions: * The 1992 Prize of the Organic Chemistry Division of the French Chemical Society. * The 1995 Clavel-Lespiau Prize of the French Academy of Science. * Chemistry Research Promotion Center of the National Science Council Fellow (Taiwan, 1997) * Astra-Zeneca USA Lecturer 1999. * Sherbrooke-Bohringer Ingelheim Canada Lecturer 2000 * Rhodia Prize 2000 * Bürgenstock Lecturer 2001 * Merck Sharpe & Dohme Lecturer 2003 * Chevalier des Palmes Académiques 2003 * Japan Society for the Promotion of Science Fellow 2004. * Organic Syntheses Distinguished Lecturer 2005 * Novartis Chemistry Lectureship 2006-2007 * Inaugural Wyeth Lecturer 2006 * Prix Dargelos 2006 * President, Bürgenstock Conference 2007 * Silver Medal CNRS 2007 * Croix de Chevalier dans l’Ordre de la Légion d’Honneur 2007 * Novartis-UC Irvine Distinguished Lecturer 2008 * Novartis-Berkeley Distinguished Lecturer 2008 * Bristol-Myers Squibb-Scripps Institute Distinguished Lecturer 2008 * Prix de l’Innovation 2008 — Ecole Polytechnique * Grignard-Wittig Award 2008 of the German Chemical Society
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
* Woodward Lecturer, Harvard University 2010 * Bohringer Ingelheim-University of British Columbia Distinguished Lecturer 2010-2011 * Honorary Member of the Sociedad Argentina de Investigación en Química Orgánica, 2011 * Fellow of the Royal Society of Chemistry, 2011 * 1st Barton Lecturer in Creativity in Organic Synthesis (2012-Imperial College) * Grand Prix Joseph-Achille Le Bel of the French Chemical Society, 2012 * Birch Lecturer, Australia National University, 2015 * Liversidge Lecturer, University of Sydney, 2015 * Elected Foreign Corresponding Member of the Academy of Sciences of Lisbon (Portugal), 2015 * Honorary Doctorate, American University of Beirut, 2016.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Free-Radical Additions to Olefins. Recent Developments and Applications
Y. Landaisa
a Institute of Molecular Sciences, University of Bordeaux, UMR-CNRS-5255, 351 cours de la libération, 33405 Talence, France
* [email protected] The regioselective free-radical addition onto olefins has attracted a considerable interest as it gives rise to useful intermediates for organic synthesis starting from readily available material.1 In this context, our laboratory has developed three-component radical functionalization of olefins, relying on the addition of two carbon fragments across the olefinic skeleton, providing adducts with two new C-C bonds along with additional functional groups. Carbo-alkynylation and carbo-oximation as well as carbo-aminomethylation were thus devised, using various olefinic partners and sulfones as radical traps.2 More recently, we extended this chemistry to the development of a one-pot carbo- alkenylation of olefins,3 as well as a useful carbo-cyanation.4 The scope and limitations of these methodologies will be discussed, along with their application to the total synthesis of natural alkaloids.5 Efforts towards the development of tin-free versions of these processes will also be disclosed.
(1) Subramanian, H.; Landais, Y.; Sibi M. P. in Comprehensive Organic synthesis, Eds. G. A. Molander, P. Knochel, 2nd ed., Vol. 4, Oxford: Elsevier, 2014, pp. 699-741. (2) (a) Godineau, E.; Landais, Y. J. Am. Chem. Soc. 2007, 129, 12662. (b) Liautard, V.; Robert, F.; Landais, Y. Org. Lett. 2011, 13, 2658. (c) Ovadia, B.; Robert, F.; Landais, Y. Org. Lett. 2015, 17, 1958. (d) Landais, Y.; Robert, F.; Godineau, E.; Huet, L.; Likhite, N. Tetrahedron 2013, 69, 10073. (e) Ovadia, B.; Robert, F.; Landais, Y. Chimia, 2016, 70, 34. (3) (a) Poittevin, C.; Liautard, V.; Beniazza, R.; Robert, F.; Landais, Y. Org. Lett. 2013, 15, 2814. (b) Beniazza, R.; Liautard, V.; Poittevin, C.; Ovadia, B.; Mohammed, S.; Robert, F.; Landais, Y. Chem. Eur. J. 2017, 23, 2439. (4) (a) Hassan, H.; Pirenne, V.; Wissing, M.; Chahinaz, K.; Hussain, A.; Robert, F.; Landais Y. Chem. Eur. J. 2017, DOI: 10.1002/chem.201605946. (b) Dange, N. S.; Robert, F.; Landais, Y. Org. Lett. 2016, 18, 6156. (5) Hassan, H.; Mohammed, S.; Robert, F.; Landais, Y. Org. Lett. 2015, 17, 4518. 15
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Prof. Yannick Landais Institute of Molecular Sciences (UMR-5255), University of Bordeaux 351, Cours de la libération, 33405 Talence, France Tel: (+33) 5 40 00 22 89; Fax: (+33) 5 40 00 62 86 Email: [email protected]
A. Personal Information Date of Birth: 09.01.1962 Place of Birth: Angers, France
B. Higher education and professional experience 1997- Professor of Organic Chemistry at the University of Bordeaux (F) 1990-97 Assistant-Professor (University of Lausanne, CH). 1994 Habilitation (University Paris-XI, Orsay, F). 1988-90 Postdoctoral fellow at the University of Cambridge (UK) with Prof. I. Fleming 1987-88 Military Service 1984-87 PhD thesis with Dr. J.-P. Robin, University Paris-XI-Orsay (F). "Recherche sur les voies d’accès aux lignanes bisbenzocyclooctadiénes et aux alcaloïdes présentant la structure biarylique pontée".
C. Fellowships, Awards and Honors 2014 Prize of the Organic Chemistry Division of the French Chemical Society (http://www.societechimiquedefrance.fr/Chimie-organique-14.html) 2014 Fellow of the French Chemical Society (1st promotion) 2000-05 Junior Member of the "Institut Universitaire de France" 1997 Alfred Werner Prize of the New Swiss Chemical Society (https://scg.ch/award) 1988-90 EU Postdoctoral Fellowship (Cambridge, UK) 1984-87 PhD Fellowship from the French “Ministère de la Recherche et de l’Enseignement Supérieur“
D. Research Interests Organosilicon Chemistry, Radical and organometallic chemistry, Organocatalysis, Asymmetric synthesis, Synthesis of natural products. See also webpage: http://ylandais.free.fr
E. Metrics 127 publications in peer-reviewed journals, 10 book chapters, 2 patents.
F. Lectures in Universities and industries 70 lectures in universities 28 Lectures in national and international congresses.
G. Selected Administrative duties 2010-14 Member of the Scientific committee of the CNRS National Institute of Chemistry (INC) 2013- President of the French-Japanese Association of Chemistry 2015- Member of the International Advisory Board of “European Journal of Organic Chemistry”
H. Supervision Supervision of 30 PhD thesis, 5 currently ongoing, and 13 post-doctoral researchers.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
α-Bromoacrylate as radical acceptor in dialkylzincs-mediated radical-polar crossover processes, theoretical investigation and synthetic applications.
Laurence Feray,* Hugo Lingua, François Vibert, Julien Maury, Eric Besson, Didier Siri and Michèle P. Bertrand
Aix Marseille Univ., CNRS, Institut de Chimie Radicalaire, UMR 7273, Equipes CMO and CT, Campus Saint- Jérôme, Avenue Normandie-Niemen, 13397 Marseille Cedex 20, France *[email protected]
Under non-degassed medium ethyl -bromoacrylate reacts with diethylzinc to give a bromocyclopropane. The reaction successively involves a radical addition followed by an SH2 at zinc, conjugate addition of the resulting enolate to the electrophilic substrate and finally a ring closure.[1] In the presence of t-butyl iodide the bromocyclopropane resulting from the addition of t-butyl radical is formed.
Theoretical calculations were performed to get a better insight into the detailed mechanism. They highlight the impact of zinc(II) chelation on the formal SH2 step.
[1] Vibert, F; Maury, J; Lingua, H; Besson, E; Siri, D; Bertrand, M.P.; Feray, L. Tetrahedron 2015, 71, 8991–9002 17
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Feray Laurence Professeur des Universités Aix-Marseille Université, Institut de Chimie Radicalaire Equipe CMO, Campus Saint-Jérôme, case 562, Marseille 33 (0)4 91 28 85 99 / 06 17 37 52 03 [email protected]
Education and scientific career
1996-2000 Ph. D. in Organic Chemistry under the direction of Pr Michèle Bertrand, Marseille. Thematic area: Triethylborane and diethylzinc in radical reactions. 2000-2001 Post-doctoral position under the direction of Pr Philippe Renaud, Fribourg, Switzerland. Thematic area : Diastereoselective 1,5-hydrogen atom transfer. 2001 Maître de conférences, Aix-Marseille Université (AMU) 2008 Habilitation à Diriger des Recherches (HDR), Marseille « Dialkylzincs in radical chemistry, synthetic applications » 2015 Professeur, Aix-Marseille Université
Research :
Development of radical methodologies based on the use of organometallic reagents. Dialkylzincs as promoters of radical-polar multicomponent reactions in aerobic medium, mechanistic studies and synthetic applications (synthesis of -lactones, lactams, pyrrolizidines, stereocontrolled synthesis of olefines…) Metal catalyzed carbozincation of various substrates
Training and administrative responsabilities in Aix-Marseille Université:
Manager of L2, L3 chemistry degree Assistant Director, departement of chemistry
Keywords:
Radical chemistry, Organometallic chemistry, Dialkylzincs, Radical-polar cascades, Multicomponent reactions.
Selected recent publications
(a) J. Maury, L. Feray, P. Perfetti, M. P. Bertrand, Org. Lett. 12 (2010) 3590. (b) J. Maury, D. Mouysset, L. Feray, S. R. A. Marque, D. Siri, M. P Bertrand, Chem. —Eur. J. 18 (2012) 3241. (c) J. Maury, L. Feray, M. P Bertrand, Org. Lett. 13 (2011) 1884. (d) J. Maury, S. Jammi, F. Vibert, S. R. A. Marque, D. Siri, L. Feray, M. P. Bertrand, J. Org. Chem. 77 (2012) 9081. (e) S. Jammi, D. Mouysset, D. Siri, M. P Bertrand, L. Feray, J. Org. Chem. 77 (2013) 1589. (f) Vibert, F.; Maury, J.; Lingua, H.; Besson, E.; Siri, D.; Bertrand, M. P.; Feray, L. Tetrahedron 2015, 71, 8991-9002.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Photoredox Catalysis for the Generation of Carbon Centered Radicals and Synthetic Applications
C. Ollivier
UPMC Univ-Paris 06 – Sorbonne Universités, Institut Parisien de Chimie Moléculaire (UMR CNRS 8232) 4 Place Jussieu, C. 229, 75005 Paris, France [email protected] Visible-light photoredox catalysis has emerged as a valuable and a greener alternative to generate radicals by single electron transfer reactions from an appropriate photocatalyst - which can be a polypyridine complex of transition metal or an organic dye - that absorbs light in the visible region. Since the pioneering studies of Kellogg, Pall and Deronzier, important contributions have been reported for synthetic purposes. In this context, we investigated various radical transformations1 involving photoreduction of ketoepoxides, ketoaziridines, onium salts and O-thiocarbamates. We took advantage of the reactivity of the photogenerated radicals to create new carbon-carbon bonds and related mechanistic studies were performed. Our next endeavors concerned the photocatalyzed oxidation of stabilized carbanions such 1,3-dicarbonyl enolates and more extensively bis- catecholato silicates. Because of their low oxidation potentials, the later have proved to be exquisite sources of radical entities which can be engaged in diverse intermolecular reactions such as vinylation, alkynylation and conjugate additions. The bis-catecholato silicates were also shown to behave as excellent partners of dual photoredox-nickel dual catalysis leading in an expeditious manner to libraries of cross coupling products.
1 For an account of this work, see: Goddard, J.-P.; Ollivier, C.; Fensterbank, L. Acc. Chem. Res. 2016, 49, 1924. 19
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Cyril OLLIVIER CNRS Research Director PhD and Habilitation Diploma (HDR) in Organic Chemistry Université Pierre et Marie Curie – Sorbonne Universités, Institut Parisien de Chimie Moléculaire (UMR 8232), 4, Place Jussieu. Case 229. Tour 32-42, 5ème étage, pièce 516, 75252 Paris Cedex 05. France Tel. ++33 (0)1 44 27 38 50 Fax ++33 (0)1 44 27 73 60, [email protected] http://www.ipcm.fr/OLLIVIER-Cyril
EDUCATION AND DIPLOMAS
Habilitation Diploma (HDR) – Accreditation to supervise research June 2013 Pierre and Marie Curie University – Sorbonne University, Paris, France
Ph.D. in Organic Chemistry - Doctor rerum naturalium December 2000 joint degree at the University of Fribourg, Fribourg, Switzerland and Pierre and Marie Curie University, Paris, France Thesis Title: Development of efficient and practical radical processes for the formation of carbon-carbon and carbon-heteroatom bonds
B.S.; M.S. in Chemistry June 1995 Pierre and Marie Curie University, Paris, France Research Interests in Master: Reactivity of hemithioketals as carbenoïds in 1,2 metallate rearrangement
CURRENT POSITION
Pierre and Marie Curie University – Sorbonne University, Paris, France October 2016 – present CNRS Research Director Research Interests: Development of new directions for research on synthetic radical and organometallic chemistry
PREVIOUS POSITIONS
Pierre and Marie Curie University, Paris, France January 2007 – September 2016 CNRS Research Fellow 1st class (Chargé de recherche) Research Interests: Development of new directions for research on synthetic radical and organometallic chemistry
Aix-Marseille University, Marseille, France October 2002 – December 2006 CNRS Research Fellow 2nd class (then 1st class in October 2006) Research Interests: Reactivity of allylsilanes and synthesis of steroids, particularly vitamin D analogs
University of Texas at Austin, Austin, TX January 2001 – September 2002 20
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
SNSF and NIH Postdoctoral fellow Advisor: Prof. Philip D. Magnus Research Interests: Approaches to the total synthesis of the diterpene antibiotic guanastepene
University of Fribourg, Fribourg, Switzerland October 1996 – December 2000 and Pierre and Marie Curie University, Paris, France Graduate Student (Swiss National Science Foundation (SNSF)) Advisors: Prof. Philippe Renaud and Prof. Max Malacria Research Interests: Organoboranes as a source of radicals, radical oxygenation and azidation
Ecole Nationale Supérieure de Techniques Avancées, Paris, France October 1995 – September 1996 Scientific Associate in Organic Chemistry Advisor: Cmdr. Dr. Laurent El Kaim Research Interests: Diazo esters addition to trifluoropyruvamides
Pierre and Marie Curie University, Paris, France October 1994 – June 1995 Master Student Advisors: Prof. Jean-François Normant and Dr. Fabrice Chemla Research Interests: Reactivity of hemithioketals as carbenoïds in 1,2 metallate rearrangement
CURRENT RESEARCH INTERESTS
Organic Synthesis Methods and Concepts. Radical Synthetic Chemistry. Organometallic Catalysis for Synthesis. Asymmetric catalysis. Eco-friendly Synthesis. Multi-step Synthesis
Green Radical Synthesis: Methods and Development of New Cascade Processes ➢ N−Acylcyanamides as new partners for radical cascade reactions. Synthesis of polyheterocyclic nitrogen-containing compounds ➢ Electron Transfert Reactions • Use of Titanium(IV) and Iron(II) complexes as new radical mediators • Development of visible-light photoredox catalysis for the generation of radicals
Transition metal catalyzed cyclization and cycloisomerisation ➢ Chiral counteranions in asymmetric catalysis
PUBLICATIONS AND BIBLIOMETRIC DATA
70 Research publications 7 Book chapters 15 International and national lectures, seminars and oral communications 35 Posters
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
New horizons for Organic Electron Donors
J. Broggi*
Aix Marseille Univ, CNRS, ICR Institut de Chimie Radicalaire, Faculté de Pharmacie, Marseille, France
The astonishing recent advances of their reactivities in fundamental organic chemistry have raised a real interest for reducing agents with totally organic neutral structures and exceptionally negative redox potentials.1 Strong organic electron donors (OEDs) are capable of single- or double-electron transfer to organic substrates under mild and homogeneous conditions, promoting bond formations through the generation of radical or anionic intermediates. Major contributions have been made in this field demonstrating the efficiency of OEDs in the selective reduction of challenging chemical bonds.2 The OEDs thus represent serious rivals to highly aggressive metal-based reducers and emerge as an attractive novel source of reducing electrons in many aspects.
Despite a great tunability, approaches involving OED-promoted electron transfers have been under-exploited, limiting the visibility of academic and industrial applications. Their convenience of manipulation and storage is still hampered by several technical parameters that could dissuade chemists of their usage. In order to extend their functionalities, our research primarily focus on the development of new methodologies, essential to outline the potential of organic electron donors. Our recent results in the development of masked OED-systems and the exploration of unprecedented applications in the field of material science will be presented.3
1For reviews, see: a) Broggi, J.; Terme, T.; Vanelle, P. Angew. Chem. Int. Ed. 2014, 53, 384. b) Murphy, J. A. In Encyclopedia of Radicals in Chemistry, Biology and Materials; Chatgilialoglu, C., Studer, A., Eds.; WILEY-VCH, Weinheim, 2012. c) Zhou, S.; Farwaha, H.; Murphy, J. A. Chimia 2012, 66, 418. d) Murphy, J. A. J. Org. Chem. 2014, 79, 3731. e) Doni, E.; Murphy, J. A. Chem. Commun. 2014, 50, 6073. 2 a) Cahard, E.; Schoenebeck, F.; Garnier, J.; Cutulic, S. P. Y.; Zhou, S.; Murphy, J. A. Angew. Chem., Int. Ed. 2012, 51, 3673. b) Farwaha, H. S.; Bucher, G.; Murphy, J. A. Org. Biomol. Chem. 2013, 11, 8073. c) Doni, E.; O’Sullivan, S.; Murphy, J. A. Angew. Chem. Int. Ed. 2013, 52, 2239. d) Doni, E.; Mondal, B.; O’Sullivan, S.; Tuttle, T.; Murphy, J. A. J. Am. Chem. Soc. 2013, 135, 10934. e) Hanson, S. S.; Richard, N. A.; Dyker, C. A. Chem. Eur. J. 2015, 21, 8052. f) Hanson, S. S.; Doni, E.; Traboulsee, K. T.; Coulthard, G.; Murphy, J. A.; Dyker, C. A. Angew. Chem. Int. Ed. 2015, 54, 11236. 3 Broggi, J.; Rollet, M.; Clément, J.L.; Canard, G.; Terme, T.; Gigmes, D.; Vanelle P. Angew. Chem. Int. Ed. 2016, 55, 5994. b) Rayala, R.; Giuglio-Tonolo, A.; Broggi, J.; Terme, T.; Vanelle, P.; Theard, P.; Médebielle, M.; Wnuk, S. F. Tetrahedron 2016, 72, 1969. 22
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BROGGI Julie Born: June 6th 1982 in Cannes, Alpes Maritimes Nationality: French Current Position Maître de Conférences (Lecturer) at the Organic Chemistry Department (Faculty of Pharmacy, AMU) Institut de Chimie Radicalaire (ICR) - UMR 7273, Equipe Pharmacochimie radicalaire (PCR), 27 Bd Jean Moulin, 13385 Marseille Cedex 5. +33 (0)4 9183 5996 / [email protected] Professional Experience 2010-2011 ATER (teaching assistant) - Laboratoire Chimie Provence (LCP), UMR 6264, Faculty of Pharmacy, Aix-Marseille II. Title: Super Electron Donors as tools in the synthesis of new nucleosidic analogues. 2009 Post-doctoral position – S. P. Nolan group Research school of chemistry, St Andrews, United Kingdom. Title: European project (EuMet): Development and application in catalysis of ruthenium complexes bearing an N-heterocyclic carbene. 2005-2008 Ph.D. - Institut de Chimie Organique et Analytique (ICOA), UMR 6005, Faculty of Science, Orléans. Title: Contribution of N-heterocyclic carbene-containing catalysts in the nucleoside chemistry. (Advisor: Prof. L.A. Agrofoglio and Dr. S. Bertaina-Raboin) 2005 Master training course - Laboratoire de Chimie des Molécules BioActives et des Arômes (LCMBA), UMR 6001, Faculty of Science, Nice. Title: Synthesis of a new AZT prodrug. Research interests JB is involved in the synthesis of novel organic reducers and their stable latent precursors. She also explores their reactivity in the reduction of uninvestigated species and for unprecedented applications including nucleoside or polymer chemistry. She is experienced in organic and medicinal compound synthesis, as well as coordination chemistry and organometallic catalysis. She is used to perform air- and moisture-sensitive experiments and handle unstable products. Scientific Publications
19 publications in peer-review journals including 3 contributions to monographs, 3 oral communications and 18 poster presentations. • Polymerization initiated by organic electron donors J. Broggi,* M. Rollet, J.-L. Clément, G. Canard, T. Terme, D. Gigmes, P. Vanelle* Angew. Chem. Int. Ed. 2016, 55, 5994-5999. • Studies toward the oxidative and reductive activation of C-S bonds in 2'-S-aryl-2'-thiouridine derivatives R. Rayala, A. Giuglio-Tonolo, J. Broggi, T. Terme, P. Vanelle, P. Theard, M. Médebielle,* S. F. Wnuk* Tetrahedron, 2016, 72, 1969-1977. • Organic electron donors as powerful single-electron reducing agents in organic synthesis
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J. Broggi,* T. Terme,* P. Vanelle* Angew. Chem. Int. Ed. 2014, 53, 384-413. • The isolation of [Pd{OC(O)H}(H)(NHC)(PR3)] (NHC = N-heterocyclic carbene) and its role in alkene and alkyne reductions using formic acid J. Broggi, V. Jurčík, O. Songis A. Poater, L. Cavallo, A. M. Z. Slawin, C. S. J. Cazin*J. Am. Chem. Soc. 2013, 135, 4588-4591. • Novel antiviral C5-substituted pyrimidine acyclic nucleoside phosphonates selected as human thymidylate kinase substrates D. Topalis, U. Pradère, V. Roy, C. Caillat, A. Azzouzi, J. Broggi, R. Snoeck, G. Andrei, J. Lin, S. Eriksson, J. A. C. Alexandre, C. El-Amri, D. Deville-Bonne, P. Meyer, J. Balzarini, L. A. Agrofoglio* J. Med. Chem. 2011, 54, 222-232.
Julie Broggi, received her M.Sc. in organic chemistry from the Université de Nice Sophia-Antipolis (France) in 2005 and then completed her Ph.D. on nucleoside chemistry in 2009 under the supervision of Prof. Luigi Agrofoglio at the Université d’Orléans (France). Her Ph.D. work focused on the applications of transition-metal complexes in the synthesis of nucleoside derivatives, such as triazolo-carbanucleosides and phosphononucleosides. These potential smallpox inhibitors were synthesized in racemic or enantioselective series. During this Ph.D., she spent some time as visiting fellow in the group of Prof. Steven P. Nolan at the Institute of Chemical Research of Catalonia (Spain). She studied the contribution of copper and palladium complexes, bearing N-heterocyclic carbene ligand, in cycloaddition, N-arylation or transfer hydrogenation reactions. For the study of their mechanism of action, she used NMR spectroscopy at variable temperature and isotopic-labelling experiments. Early 2009, she moved to the School of Chemistry of the University of St Andrews (UK) to continue working with Prof. Nolan as post-doctoral fellow. She worked on the synthesis of imidazolium salts and the corresponding free carbenes along with the synthesis of ruthenium catalysts and their applications in metathesis reactions. In the context of a metathesis European network (project EUMET - CP-FP 211468- 2), she supervised the training of junior group members. In 2010, she was appointed ATER and then Maître de Conférences (Lecturer) in the PCR group of the Institut de Chimie Radicalaire (ICR). She is involved in the synthesis of novel organic electron donors and their stable latent precursors. These new organic reducers are used as powerful and selective alternative tools to metallic derivatives in reduction strategies through single- or double-electron transfers. she also explores their reactivity in the reduction of uninvestigated functional groups and for unprecedented applications including nucleoside or polymer chemistry.
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Photopolymerization initiators: Synthesis and photochemical studies
D. Gigmes
Aix Marseille Univ, CNRS, Institut de Chimie Radicalaire, Marseille, France
Nowadays, photoinitiated polymerization is one of the preferred techniques for a large range of applications such as coatings, inks and adhesives, dentistry, microelectronics, laser direct imaging technology and 3D printing.1-3 Indeed, photopolymerization presents several advantages such as fast polymerization kinetics even at room temperature, the absence of solvents limiting the formation of volatile organic compounds and the possibility to irradiate with high precision specific zones allowing the construction of tailored patterns. However, the employment of UV light, generally required for this technique, remains a major issue due to its high energy and the toxicity of the associated irradiation sources. To overcome this drawback, photoinitiating systems able to initiate polymerization under soft light irradiation sources is currently the subject of intense efforts.3 In this context, recently we have synthesized a large library of photosensitive molecules based on naphthalimide and diketopyrrolopyrrole derivatives exhibiting for some of them a remarkable effiency to initiate the polymerization under soft irradiation sources.4,5 Hence, in this communication, the synthesis and the polymerization abilities of the most relevant prepared compounds as well as their photochemical behaviour will be presented.
References 1. Fouassier, J. P.; Lalevée, J. Photoinitiators for Polymer Synthesis: Scope, Reactivity and Efficiency; Wiley-VCH: Weinheim, Germany, 2012. 2. Dadashi-Silab, S.; Doran, S.; Yagci, Y. Chem. Rev. 2016, 116, 10212–10275. 3. Xiao, P.; Zhang, J.; Dumur, F.; Tehfe, M. A.; Morlet-Savary, F.; Graff, B.; Gigmes, D.; Fouassier, J. P.; Lalevée, J. Prog. Polym. Sci. 2015, 41, 32-66. 4. Zhang, J.; Zivic, N.; Dumur, F.; Xiao, P.; Graff, B.; Fouassier, J. P.; Gigmes, D.; Lalevée, J. Polymer, 2014, 55, 6641-6972. 5. Zivic, N.; Bouzrati-Zerrelli, M.; Villotte, S.; Morlet-Savary, F.; Dietlin, C.; Dumur, F.; Gigmes, D.; Fouassier, J.P.; Lalevée, J. Polym. Chem. 2016, 7, 5873-5879.
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Didier Gigmes completed his PhD in organic chemistry in 1998 under the supervision of Prof. Paul Tordo at the University Paul Cézanne in Marseille (France). Then he moved to Elf Atochem North America in Pennsylvania (King of Prussia, PA, USA) to work as a post-doc in the field of controlled radical polymerization using cobalt derivatives. In 2001, he was recruited as researcher at CNRS to develop the nitroxide-mediated polymerization (NMP) technique. In 2008, he defended his Habilitation at the University of Provence (Marseille, France) and in October 2010, he was appointed Research Director at the CNRS working at Aix-Marseille University (Marseille, France). Currently, with his research group his main concerns are focused on the development and use of new methodologies for the synthesis of advanced polymer materials. He is also involved in the development of original methodologies for Nitroxide Mediated Photopolymerization and the synthesis of versatile photo-initiators. DG is (co)author of 270 peer review articles in international journals, 15 patents, 10 book chapters and editor of one book on NMP. In 2013, he was awarded by the Société Chimique de France as « Junior Distinguinshed Member ».
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Organic and Polymer Free-radical Synthesis using NHC–Boranes
E. Lacôte;a D. P. Curran;b J. Lalevéec; M. Lansalotd and E. Bourgeat-Lami,d
aCNRS, Université Claude Bernard Lyon 1, Villeurbanne, France bUniversity of Pittsburgh (PA), USA cENSCMu, Université de Haute-Alsace, Mulhouse, France dCNRS, CPE Lyon, Villeurbanne, France
Complexation of boron with N-Heterocyclic carbenes stabilizes boryl radicals and makes them planar -type radicals. This has important consequences for the reactivity of NHC-borane complexes. The radical stabilization ensures that they can be introduced in organic free-radical synthesis and the donation makes the NHC-boryl radicals nucleophilic.
In the talk we will show that NHC-boranes are exquisite reagents for organic reactions and photopolymerization in organic and disperse media.
• S.-H. Ueng, M. Makhlouf Brahmi, É. Derat, L. Fensterbank, E. Lacôte, M. Malacria, D. P. Curran, J. Am. Chem. Soc. 2008, 130, 10082-10083, DOI: 10.1021/ja804150k. • S. Telitel, A.-L. Vallet, S. Schweizer, B. Delpech, N. Blanchard, F. Morlet-Savary, B. Graff, D. P. Curran, M. Robert, E. Lacôte, J. Lalevée, J. Am. Chem. Soc. 2013, 135, 16938-16947, DOI: 10.1021/ja4066267 • S. Telitel, A.‐L. Vallet, D. M. Flanigan, B. Graff, F. Morlet‐Savary, T. Rovis, J. Lalevée, E. Lacôte, Chem. Eur. J. 2015, 21, 13772-13777, DOI: 10.1002/chem.201500499.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Emmanuel Lacôte
EDUCATION AND EMPLOYMENT 2015-present : University of Lyon, Univ. Claude Bernard Lyon 1, (department for hydrazines and polynitrogen energetic compounds), Villeurbanne ; Chair. 2013 : promoted directeur de recherche 1st class, CNRS. 2012 : University of Lyon, CPE Lyon, (department for chemistry, catalysis, polymers and processes), Villeurbanne. 2011 : appointed group leader, Inst. de chimie des subst. naturelles (CNRS), Gif s/ Yvette. 2008 : promoted directeur de recherche 2nd class, CNRS. 2004 : promoted chargé de recherche 1st class, CNRS. 2004 : Habilitation, Université Pierre et Marie Curie, defended September 27. 2000 : appointed chargé de recherche 2nd class, CNRS, U. Pierre et Marie Curie, Paris. 1999-2000 : Postdoctoral fellow, Stanford University, USA (Paul A. Wender). Total Synthesis of Bryostatin 1 Analogs. 1999 : Ph. D. (joint degree), Université Pierre et Marie Curie / Université de Fribourg (Switzerland), Advisors: Max Malacria, Philippe Renaud. Applications of Lewis acids in radical chemistry. Defended June 29, 1999. 1991-1995 : undergraduate studies, École Normale Supérieure, Paris
AWARDS 2016 : Bessel Award for research, Alexander v. Humboldt Foundation (Germany) 2012 : JSPS fellow (Chuo University, Tokyo, Japan) 2010 : Scholar in residence, Center of Excellence of the School of Sciences, Tokyo (Japan) 2010 : Excellence in research award, CNRS (PES, first call, renewed 2015). 2009 : Actelion Chair (ENSC Mulhouse) 2003 : Young investigator travel award, 38th Conference on Stereochemistry, Bürgenstock, Suisse 1999 : Lavoisier postdoctoral fellowship (French governement, declined), Cancer research fund award.
INVITED POSITIONS • 2016: Queen's University, Kingston (ON, Canada) • 2014: Osaka Prefecture University (Japan) • 2012: Westfälische Wilhelms-Universität Münster (Germany) • 2010: University of Tokyo (Japan) • 2010: ENSCMu (France)
5 REPRESENTATIVE PUBLICATIONS
9– 1) "Grafting of Secondary Diol-Amides onto [P2W15V3O62] Generates Hybrid Heteropoly Acids" Lachkar, D.; Vilona, D.; Dumont, E.; Lelli, M.; Lacôte, E. Angew. Chem. Int. Ed. 2016, 55, 5961-5965; DOI: 10.1002/anie.201510954. 2) "Polyboramines: Polymers featuring Lewis Pairs in their backbone for Hydrogen Release" Ledoux, A.; Larini, P.; Boisson, C.; Monteil, V.; Raynaud, J.; Lacôte, E. Angew. Chem. Int. Ed. 2015, 54, 15744-15749; DOI: 10.1002/anie.201508395. VIP paper (top 5% Angewandte accepted manuscripts). 3) "Formation of NHC-Boryl Radicals through Electrochemical and Photochemical Cleavage of the B–S bond in N-Heterocyclic Carbene-Boryl Sulfides" Telitel, S.; Vallet, A.-L.; Schweizer, S.; Delpech, B.; Blanchard, N.; Morlet-Savary, F.; Graff, B.; Curran, D. P.; Robert, M.; Lacôte, E.; Lalevée, J. J. Am. Chem. Soc. 2013, 135, 16938-16947; DOI: 10.1021/ja4066267.
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4) "NHC-Boranes Accelerate Type I Radical Photopolymerizations and overcome Oxygen Inhibition" Lalevée, J.; Telitel, S.; Tehfe, M.-A.; Fouassier, J. P.; Curran, D. P.; Lacôte, E. Angew. Chem. Int. Ed. 2012, 51, 5958-5961. 5) "Complexes of Borane and N-Heterocyclic Carbenes (NHC Boranes): A New Class of Radical Hydrogen Atom Donor" Ueng, S.-H.; Makhlouf Brahmi, M.; Derat, É.; Fensterbank, L.; Lacôte, E.; Malacria, M.; Curran, D. P. J. Am. Chem. Soc. 2008, 130, 10082-10083.
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Molecular Catalysis of the Photochemical Reduction of CO2 into CO and beyond: on the Road to Solar Fuels
J. Bonin,* H. Rao and M. Robert
Université Paris Diderot, Sorbonne Paris Cite, Laboratoire d’Electrochimie Moléculaire UMR 7591 CNRS, 15 rue Jean-Antoine de Baïf, 75205, Paris Cedex 13 *[email protected] Facing the current environmental and energy issues, the activation of small molecules such as water, oxygen and carbon dioxide represents a main research challenge.1 In particular, the generation of solar fuels, namely hydrogen, carbon monoxide, methane or methanol, using catalysts made of abundant and non-toxic materials and with a minimum energy input is a long term strategic objective. To efficiently convert electrons into chemical energy stored in molecular bonds, either by electrochemical or photochemical ways, processes require a selective and robust catalysis, which necessitates its intimate understanding at the molecular scale. In this presentation, I will present both fundamental and applied studies developed at LEM on the use of molecular homogeneous catalysts based on fourth-period transition metals (Fe, Co, Ni), 2 3-6 and in particular iron porphyrins, to catalyze the photochemical reduction of CO2 into CO, and beyond.7
(1) Tatin, A.; Bonin, J.; Robert, M. ACS Energy Lett. 2016, 1, 1062. (2) Bonin, J.; Maurin, A.; Robert, M. Coord. Chem. Rev. 2016, DOI: 10.1016/j.ccr.2016.09.005. (3) Bonin, J.; Chaussemier, M.; Robert, M.; Routier, M. ChemCatChem 2014, 6, 3200. (4) Bonin, J.; Robert, M.; Routier, M. J. Am. Chem. Soc. 2014, 136, 16768. (5) Chen, L.; Guo, Z.; Wei, X.-G.; Gallenkamp, C.; Bonin, J.; Anxolabéhère-Mallart, E.; Lau, K.-C.; Lau, T.-C.; Robert, M. J. Am. Chem. Soc. 2015, 137, 10918. (6) Rao, H.; Bonin, J.; Robert, M. Submitted. (7) Bonin, J.; Schmidt, L. C.; Rao, H.; Robert, M. Submitted.
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Dr. Julien BONIN Associate Professor of Chemistry Université Paris Diderot Laboratoire d'Electrochimie Moléculaire – UMR 7591 15 Rue Jean-Antoine de Baïf 75205 Paris Cedex 13, France Tel: (33) 1 57 27 87 93 Fax: (33) 1 57 27 87 88 http://www.lemp7.cnrs.fr/
Academic background 2016 / Habilitation à Diriger des Recherches. June 2012 / Invited scientist, Instituto de Investigaciones en Fisico-química, Universidad Nacional de Córdoba, Argentina. December 2011 / Invited scientist, Ångström Laboratory, Uppsala University, Sweden. Mai-June 2010 / Invited scientist, Department of Chemistry, Massachusetts Institute of Technology, USA. Since Sept. 2006 / Associate Professor of Chemistry, LEM, Université Paris Diderot. 2005-2006 / Postdoctoral Research Associate, Radiation Laboratory, of Notre Dame, USA. 2002-2005 / PhD in Molecular Physical Chemistry, Laboratoire de Chimie Physique, Université Paris Sud 11.
Bibliographic records 26 publications
Research themes Fundamental approaches of photochemical processes Proton-coupled electron transfers Photoinduced electron transfers and bond-breaking Small molecule activation such as CO2 and protons reduction
Recent publications
1) Rao, H., Bonin, J. & Robert, M. “Non-sensitized Selective Photochemical Reduction of CO2 to CO under Visible Light with an Iron Molecular Catalyst”, Chem. Commun. 53, 2830-3, 2017. 2) Bonin, J., Maurin, A. & Robert, M., “Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO2 with Fe and Co Metal Based Complexes. Recent Advances”, Coord. Chem. Rev. 334, 184-98, 2017. 3) Tatin, A., Bonin, J. & Robert, M., “A Case for Electrofuels”, ACS Energy Lett. 1, 1062-4, 2016. 4) Rao, H., Yu, W.-Q., Zheng, H.-Q., Bonin, J., Fan, Y.-T., Hou, H.-W., “Highly Efficient Photocatalytic Hydrogen Evolution from Nickel Quinolinethiolate Complexes under Visible Light Irradiation”, J. Power Sources 324, 253-60, 2016. 5) Chen, L., Guo, Z., Wei, X.-G., Gallenkamp, C., Bonin, J., Anxolabéhère-Mallart, E., Lau, K.-C., Lau, T.- C. and Robert, M., “Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO2 with Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal Center”, J. Am. Chem. Soc. 137, 10918-21, 2015. 31
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Surface functionalization by model complexes of copper enzymes: the “self- induced electroclick” approach
N. Le Poula,*
aLaboratoire CEMCA, UMR CNRS 6521, Université de Bretagne Occidentale, Brest, France *[email protected] The immobilization of biomimetic redox devices onto solid supports is of particular importance for the development of efficient sensors and catalysts. It also raises the fundamental question of coupled electron transfer to reactivity at a metal center. An appealing strategy to address this issue is to graft a metal center in a well pre-organized and controlled way, such as in self-assembled monolayers (SAMs). In this context, we have developed a procedure based on the self-induced electrochemical immobilization of Cu complexes onto pre-modified gold electrodes through a Cu(I)-catalyzed azide-alkyne Huisgen 1,3-dipolar cycloaddition (“electroclick” reaction).1 Several molecular and supramolecular biomimetic complexes have been successfully grafted according to this approach.2-3 Two types of applications have been tested: catalytic reduction of nitrite ions4 and selective detection of alkylamines5 (Figure) in an aqueous medium.
References 1. Gomila, A.; Le Poul, N.; Cosquer, N.; Kerbaol, J. M.; Noel, J. M.; Reddy, M. T.; Jabin, I.; Reinaud, O.; Conan, F.; Le Mest, Y., Dalton Trans. 2010, 39 (48), 11516-11518. 2. Orain, C.; Le Poul, P.; Le Mest, Y.; Le Poul, N., J. Electroanal. Chem. 2013, 710, 48-58. 3. Orain, C.; Le Poul, N.; Gomila, A.; Kerbaol, J. M.; Cosquer, N.; Reinaud, O.; Conan, F.; Le Mest, Y., Chem. Eur J. 2012, 18 (2), 594-602. 4. Orain, C.; Porras-Gutiérrez, A. G.; Evoung Evoung, F.; Charles, C.; Cosquer, N.; Gomila, A.; Conan, F.; Le Mest, Y.; Le Poul, N., Electrochem. Commun. 2013, 34, 204-207. 5. De Leener, G.; Evoung-Evoung, F.; Lascaux, A.; Mertens, J.; Porras-Gutierrez, A. G.; Le Poul, N.; Lagrost, C.; Over, D.; Leroux, Y. R.; Reniers, F.; Hapiot, P.; Le Mest, Y.; Jabin, I.; Reinaud, O.,. J. Am. Chem. Soc. 2016, 138 (39), 12841-12853. 32
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Nicolas LE POUL (born 1975) CNRS Researcher (CR1) since 2006, Laboratory CEMCA UMR 6521 CNRS, University of Brest [email protected]; Web page (UBO)
EDUCATION Master degree (1998), University of Rennes (FR) Ph.D thesis (2001), University of Exeter (UK)
EXPERIENCES Ph.D Thesis in Physical Chemistry (2001)“Charge transfer at the HTSC/liquid electrolyte interface” (University of Exeter (UK), Dr. S.J. Green) Post-doctoral assistant (2002). “Ions sensors based on cathode phosphate materials”(University of Amiens (FR), UMR CNRS 6007, Pr J.-M. Tarascon) Post-doctoral assistant (2004). “Electrochemical studies of synthetic models of copper enzymes” (University of Brest (FR), UMR CNRS 6521, Dr. Y. Le Mest) Research engineer (2005). “Post-mortem studies of Li-ion batteries” (BATSCAP-BOLLORE (FR))
RESEARCH AREA Electrochemistry of inorganic complexes and organic species ; Spectroelectrochemistry; Cryo-spectroelectrochemistry, Surface functionalization; Electrocatalysis.
SCIENTIFIC ACTIVITY 40 publications in international journals with peer view; Yearly participation to international meetings (oral communication).
SELECTED PUBLICATIONS • "Immobilization of monolayers incorporating Cu funnel complexes onto gold electrodes. Application to the selective electrochemical recognition of primary alkylamines in water", G. De Leener, F. Evoung−Evoung, A. Lascaux, J. Mertens, A. G. Porras−Gutiérrez, N. Le Poul, C. Lagrost, D. Over, Y. R. Leroux, F. Reniers, P. Hapiot, Y. Le Mest, I. Jabin, O. Reinaud, J. Am. Chem. Soc. 2016, 138, 12841−12853. • "Room−temperature characterization of a mixed−valent µ−hydroxodicopper(II,III)", J. A. Isaac, F. Gennarini, I. Lopez, A. Thibon−Pourret, R. David, G. Gellon, B. Gennaro, C. Philouze, F. Meyer, S. Demeshko, Y. Le Mest, M. Reglier, H. Jamet, N. Le Poul, C. Belle, Inorg. Chem. 2016, 55, 8263−8266. • "Supramolecular modeling of mono-copper enzyme active sites with calix[6]arene-based funnel complexes", N. Le Poul, Y. Le Mest, I. Jabin, O. Reinaud, Acc. Chem. Res. 2015, 48, 2097-2106. • "Electrochemically and chemically induced redox processes in molecular machines", N. Le Poul, B. Colasson , ChemElectrochem 2015, 2, 475-496.
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• "Electrocatalytic reduction of nitrite ions by a copper complex attached as SAMs on gold by “self- induced electroclick”: Enhancement of the catalytic rate by surface coverage decrease", C. Orain, A. G. Porras-Gutiérrez, F. Evoung Evoung, C. Charles, N. Cosquer, A. Gomila, F. Conan, Y. Le Mest, N. Le Poul, Electrochem. Commun. 2013, 34, 204-207.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Electron-triggered metamorphism in viologen-based (supra)molecular materials
C. Kahlfussa, E. Saint-Amanb, E. Dumonta and C. Buchera * aUniv Lyon, Ens de Lyon, CNRS UMR 5182, Université Claude Bernard Lyon 1, Laboratoire de Chimie, F69342, Lyon, France. bUniversité Grenoble-Alpes, CNRS, Département de Chimie Moléculaire (UMR 5250), F38400, Grenoble, France. *[email protected] The ability to control the structure and organization of molecular materials has emerged in the past decade as a major scientific objective that is mainly motivated by exciting foreseeable applications in nanoscience. Enormous technologic interests are for instance at stake in being able to devise molecular objects that could respond to external stimuli by changes in structure and function. These particular properties can lead to applications in various domains as (i) in molecular electronics, (ii) in analytic science, with switchable hosts allowing the controlled binding/release of pollutants or drugs, (iii) in materials science with the development of adaptive supramolecular polymers. In this lecture, the syntheses and detailed physico-chemical properties of a series of switchable molecular architectures whose movements can be triggered by electrochemically driven self- assembly of organic radicals will be presented.1-8 Particular emphasis will be given to electron- responsive tweezer-like molecules allowing to control the organization within self-assembled coordination oligomers/polymers. The dynamic properties of these redox-responsive molecular architectures and molecular materials will mainly be discussed on the basis of electrochemical, spectroelectrochemical and ESR experiments supported by quantum chemical calculations. +ne
n -ne
References (1) Kahlfuss, C.; Saint-Aman, E.; Bucher, C. “Redox-controlled intramolecular motions triggered by -dimerization and pimerization “ In Organic Redox Systems: Synthesis, Properties, and Applications; Nishinaga, T., Ed.; John Wiley and sons, 2016. (2) Iordache, A.; Oltean, M.; Milet, A.; Thomas, F.; Baptiste, B.; Saint-Aman, E.; Bucher, C. J. Am. Chem. Soc. 2012, 134, 2653. (3) Iordache, A.; Kanappan, R.; Métay, E.; Duclos, M.-C.; Pellet-Rostaing, S.; Lemaire, M.; Milet, A.; Saint-Aman, E.; Bucher, C. Org. Biomol. Chem. 2013, 11, 4383. (4) Kahlfuss, C.; Métay, E.; Duclos, M.-C.; Lemaire, M.; Milet, A.; Saint-Aman, E.; Bucher, C. Chem. Eur. J. 2014, 21, 2090; ibid C. R. Chimie 2014, 17, 505. (5) Kahlfuss, C.; Milet, A.; Wytko, J. ; Weiss, J.; Saint-Aman, E.; Bucher, C. Org. Lett., 2015, 17 , 4058. (6) Iordache, A.; Retegan, M.; Thomas, F.; Royal, G.; Saint-Aman, E.; Bucher, C. Chem. Eur. J. 2012, 18, 7648. (8) Kahlfuss, C.; Denis-Quanquin, S.; Calin, N.; Dumont, E.; Garavelli, M.; Royal, G.; Cobo, S.; Saint-Aman, E.; Bucher, C. J. Am. Chem. Soc. 2016, 138, 15234. 35
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
CHRISTOPHE BUCHER, PhD Research Director at the National Council for Scientific Research. Department of Chemistry “Supramolecular and Biorganic Chemistry” Group Ecole Normale Supérieure de Lyon [email protected] SCF membership N°: 26545 Tel : +(0033) 472 728 864 ; Fax : +(0033) 472 728 860
Dr. Christophe Bucher, 45 years old, obtained a Ph.D. in Physical chemistry from the University of Burgundy at Dijon in 1999 (supervisor: Dr. Jean Michel Barbe). His thesis work involved investigations on the catalytic properties of iron and cobalt cyclam complexes. He was then Postdoctoral Fellow with Professor Jonathan Sessler at the University of Texas at Austin from Nov.1999 to Sept. 2001 working on pyrrole-based macrocycles and cryptands for applications in anion sensing. He started his academic career in 2001 as a CNRS researcher at the University Joseph Fourier-Grenoble in the Laboratory of Organic Electrosynthesis and Redox Photochemistry which became in 2005 the Department of Molecular Chemistry. In 2008 he obtained a HDR diploma delivered by the University of Grenoble. He joined the Ecole Normale Supérieure in Lyon in 2012 where he currently develops his own research activity as a senior CNRS researcher (http://www.ens-lyon.fr/CHIMIE/). He has a fully pluridisciplinary background with expertise ranging from organic synthesis, coordination chemistry and supramolecular chemistry to advanced physical chemistry including molecular/analytical electrochemistry and surface modification. His current fields of interest cover different aspects of supramolecular chemistry, including the design, synthesis and applications of electron-switchable molecular and supramolecular materials with particular emphasis on molecular hosts featuring e-switchable recognition properties and on e- responsive self-assembled supramolecular materials. Since 2004, he has been involved in teaching electrochemistry at ENS-Lyon at the undergraduate and postgraduate levels. He is also involved since 2012 as an expert in molecular electronics for the “Observatoire des Micro et Nanotechnologies (OMNT). Since 2014, he is member of the scientific board of the institute of chemistry in Lyon (ICL) and member of the local board of the French Chemical Society (SCF, Section Rhône-Alpes).
FIELDS OF INTEREST & EXPERTISE Supramolecular Chemistry & Electrochemistry – Switchable Molecular and Supramolecular Materials – Molecular Machinery – Host-Guest Chemistry – Redox Activation and Sensing .
PUBLICATION METRICS/AWARDS C. Bucher is author or co-author of two book chapters, one patent and of more than 80 articles in peer reviewed international journals. ORCID ID : orcid.org/0000-0003-1803-6733 He has received in 2011 the Young researcher award from the French division of the International Society of Electrochemistry. 36
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Photo-induced redox catalysis for hydrogen production with molecular compounds
M.-N. Collomb;a* R. Gueret;a C. E. Castillo;a T. Stoll;a J. Chauvin,a F. Odobel,b M. Sliwa,c P. Lainé,d and J. Fortagea
a Université Grenoble Alpes, CNRS, DCM, UMR 5250, F-38000 Grenoble, France bUniversité Nantes, Univ LUNAM, CEISAM, CNRS,UMR 6230, F-44322 Nantes 3, France cUniversité Lille 1, CNRS, LASIR, UMR 8516, 59655 Villeneuve d’Asq, France dUniversité Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR CNRS, 15 rue J-A de Baïf, 75013 Paris, France * [email protected]
Solar driven water-splitting into hydrogen and oxygen, also referred as artificial photosynthesis, has emerged as a very attractive sustainable approach to produce the fuel H2. Molecular approaches to generate H2 photochemically typically involve the association of three-components, a light- harvesting antenna (photosensitizer), a H2-evolving catalyst, and a sacrificial electron donor in homogeneous solution.1 If a large number of such photocatalytic systems have been reported, very few of them are able to operate in pure aqueous solution, without co-organic solvent, because of the lower stability/solubility of molecular compounds in water. However, this is an important requirement for their further applications in photoelectrochemical water-splitting devices. This talk 2 will present our efficient systems for the visible-light-driven H2 production in water using rhodium 3 2+ and cobalt complexes as catalysts and [Ru(bpy)3] as photosensitizer in the presence of ascorbate as sacrificial electron donor. The advantages of coupling catalyst and photosensitizer by a covalent bond will be also presented as well as our promising results towards the development of systems only based on earth abundant elements by using a new water soluble organic dye which represents a very 2+ attractive alternative to [Ru(bpy)3] .
Acknowledgments: The authors wish to thank for financial supports the LABEX ARCANE (ANR-11-LABX-0003-
01) for the project H2Photocat and the French National Research Agency for the project HeteroCop (ANR-09-BLAN- 0183-01). This work was also supported by COST CM1202 program (PERSPECT H2O).
1 (a) Stoll, T.; Castillo, C. E.; Kayanuma, M.; Sandroni, M.; Daniel, C.; Odobel, F.; Fortage, J.; Collomb, M.-N., Coord. Chem. Rev., 2015, 304– 305, 20-37. (b) Queyriaux, N.; Kaeffer, N.; Morozan, A.; Chavarot-Kerlidou, M.; Artero V., J. Photochem. Photobiol. C: Photochem. Rev., 2015, 25, 90-105. 2 (a) Stoll, T.; Gennari, M.; Serrano, I.; Fortage, J.; Chauvin, J.; Odobel, F.; Rebarz, M.; Poizat, O.; Sliwa, M.; Deronzier A.; Collomb M.-N., Chem. Eur. J., 2013, 19, 782-792. (b) Stoll, T.; Gennari, M.; Fortage, J.; Castillo, C. E.; Rebarz, M.; Sliwa, M.; Poizat, O.; Odobel, F.; Deronzier A.; Collomb, M.-N., Angew. Chem., Int. Ed. Engl., 2014, 53, 1654-1658. 3 (a) Varma, S.; Castillo, C. E.; Stoll, T.; Fortage, J.; Blackman, A. G.; Molton, F.; Deronzier A.; Collomb, M.-N. PhysChemChemPhys, 2013, 15, 17544-17552. (b) Gimbert-Surinach, C.; Albero, J.; Stoll, T.; Fortage, J.; Collomb, A. Deronzier, E. Palomares and A. Llobet, J. Am. Chem. Soc., 2014, 136, 7655-7661. (c) R. Gueret, C. E. Castillo, M.-N.; Rebarz, M.; Thomas, F.; Hargrove, A.-A.; Pécaut, J.; Sliwa, M.; Fortage J.; Collomb M.-N., J. Photochem. Photobiol., B, 2015, 152, Part A, 82-94. 37
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Marie-Noëlle COLLOMB
Marie-Noëlle Collomb, 50 ys. old, is Research Director 2nd class at the CNRS. She is the leader of the group «Artificial photosynthesis and energy carriers» in the Chimie Inorganique Rédox laboratory (CIRE) at the Département of Chimie Moléculaire (DCM), Université Grenoble Alpes. She received her Ph. D. from the Université Joseph Fourier (UJF) of Grenoble in 1993 under the supervision of Alain Deronzier, in the field of electrocatalytic carbon dioxide reduction with ruthenium carbonyl complexes. After a year working in the group of Prof. Marc Fontecave on alkanes oxidation catalysis as lecturer at UJF (1993-94), she joined the CNRS in 1994 as research scientist at UJF. In 1998-99, as a CNRS research associate (NATO fellowship), she joined the groups of Profs R. H. Crabtree and G. W. Brudvig at Yale University (New Haven, USA) to develop bioinspired manganese complexes for water oxidation. She was appointed CNRS Research Director in 2007. Her background ranges from coordination chemistry, electrochemistry and photo-induced redox catalysis. Her current research interest deals with the development of electrocatalytic and photocatalytic systems based on transition metal complexes and recently on (oxide) metallic nanoparticles for artificial photosynthesis applications (H2 production by water reduction and water oxidation) in homogeneous and in heterogeneous phase (surface modified electrodes, semi-conductor based photocathodes and photoanodes).
She has supervised 10 PhD thesis, 10 post-doctoral and more than 30 undergraduate and graduate fellows. She is the author of 101 publications (h-index: 32, (ISI WEB of Knowledge)), two patents, 1 encyclopedia chapter, and had more than 30 invitations in national and international conferences (conferences/keynotes/lectures) and in Universities. She is and has been involved as coordinator and partner in several national and international programs (ANRs (JCJC, blanche), Arcane Labex, CNRS-CONICYT and ECOS Sud-CONICYT (Chili), Hubert Curien (New-zealand)…). She is also involved as a partner in a COST
ACTION CM1202 « PERSPECT-H2O: Supramolecular photocatalytic water-splitting” and member of the GDR solar fuels. She has fruitful national and international collaborations (Germany (MPI for Chemical Energy Conversion, Mulheïm, F.Neese, S. DeBeer, D. Pantazis), Spain (ICIQ Tarragona, A. Llobet, Univ. of Girona, M. Romero), New-Zealand (Univ. of Auckland, A. G. Blackman), Chili (Univ. of Conception, B. Luis RIVAS)). She also assumes different responsibilities, e.g. member of the Scientific Council of the French ANR program "CES06 - Chemistry" (2014), member of the Scientific Council of the French LABEX program ARCANE (since 2012), member of the Council of the Institute of Molecular Chemistry of Grenoble (2012-2016) and of the DCM (since 2016), expert for research agencies.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Engineering of photocatalytic reactions in microreactors
Timothy Noël*
*Eindhoven University of Technology, Micro Flow Chemistry & Process Technology, Eindhoven, The Netherlands. [email protected]
Photoredox catalysis is emerging as a new and powerful tool in synthetic organic chemistry to facilitate photochemical reactions by means of visible light.[1] Notable examples involve the use of ruthenium(II)polypyridine complexes which upon irradiation produce a photoexcited state. This photoexcited state gives rise to a single electron transfer process (SET) with organic substrates which can undergo subsequently a synthetic transformation. Whereas a myriad of different reactions have recently succumbed to this mode of catalysis, it is important to note that several challenges still remain with respect to high catalyst loadings, extended reaction times, scalability, and generality of the catalyst system.
In this oral communication, we will report on the acceleration of gas-liquid photocatalytic reactions in continuous photomicroreactors.[2] We will go into detail on both engineering and chemical/catalytic aspects of continuous-flow photochemistry. Relevant examples from our group will be detailed on during the presentation.[3] Also, we will report on the development of a solar photomicroreactor, which allows the efficient harvesting of solar energy for photocatalytic transformations.[4]
[1] For some general reviews on photoredox catalysis: (a) D. M. Schultz and T. P. Yoon, Science, 2014, 343, 1239176. (b) N. A. Romero and D. A. Nicewicz, Chem. Rev., 2016, 116, 10075-10166. (c) C. K. Prier, D. A. Rankic and D. W. C. MacMillan, Chem. Rev., 2013, 113, 5322-5363. [2] For reviews on continuous-flow photochemical processes: (a) D. Cambie, C. Bottecchia, N. J. W. Straathof, V. Hessel, T. Noël, Chem. Rev. 2016, 116, 10276-10341. (b) Y. Su, N. J. W. Straathof, V. Hessel, T. Noël, Chem. Eur. J. 2014, 20, 10562-10589. [3] For selected work on photoredox catalysis from our group: (a) N. J. W. Straathof, S. E. Cramer, V. Hessel, T. Noël, Angew. Chem. Int. Ed. 2016, 55, 15549-15553. (b) Y. Deng, X.-J. Wei, H. Wang, Y. Sun, T. Noël, X. Wang, Angew. Chem. Int. Ed. 2017, 55, 832-836. (c) C. Bottecchia, N. Erdmann, P. M. A. Tijssen, L.-G. Milroy, L. Brunsveld, V. Hessel, T. Noël, ChemSusChem 2016, 9, 1781-1785. (d) N. J. W. Straathof, B. J. P. Tegelbeckers, V. Hessel, X. Wang, T. Noël, Chem. Sci. 2014, 5, 4768-4773. (e) N. J. W. Straathof, H. P. L. Gemoets, X. Wang, J. C. Schouten, V. Hessel, T. Noël, ChemSusChem 2014, 7, 1612-1617. (f) X. Wang, G. D. Cuny, T. Noël, Angew. Chem. Int. Ed. 2013, 52, 7860-7864. [4] D. Cambie, F. Zhao, V. Hessel, M. G. Debije, T. Noël, Angew. Chem. Int. Ed. 2017, 56, 1050-1054 39
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Dr. Timothy Noël
Name Timothy Noël Nationality Belgian Address Laboratory of Micro Flow Chemistry & Process Technology, Eindhoven University of Technology, STO 1.37, PO Box 513, 5600 MB Eindhoven, The Netherlands. E-mail [email protected] Website www.NoelResearchGroup.com Professional experience
2012-present Tenured Assistant Professor (Dept. of Chemical Engineering, TU Eindhoven) • my research group is focused on the combination of reaction engineering, process technology, organic synthetic chemistry and material science. 2010-2011 Post-doctoral researcher (Massachusetts Institute of Technology, Cambridge, USA) • Host: Prof. Dr. Stephen L. Buchwald (Dept. of Chemistry) and collaboration with Prof. Dr. Klavs F. Jensen (Dept. of Chemical Engineering). Education 2000-2004 M.Sc. Industrial Chemical Engineer (KaHo Sint Lieven, Ghent, Belgium) 2005-2009 Ph.D. in Organometallic Chemistry (Ghent University, Ghent, Belgium) • Supervisor: Prof. Dr. Johan van der Eycken Current Projects 2016 FET Open, NOW, co-applicant (Prof. Hessel Coordinator). 3900 Catalyst Cascade Reactions in ‘One-Flow’ within a Compartmentalized, k€ Green-Solvent ‘Digital Synthesis Machinery’ – End-to-End Green Process Design for Pharmaceuticals 2015 VIDI award from Dutch Science Foundation, NWO, personal grant. 800 k€ Sensitized photoredox catalysis in continuous-flow microreactors 2015 Marie Curie Innovative Training Network, coordinator of the project. 2,289 Accelerating photoredox catalysis in continuous-flow systems k€ 2013 ECHO grant from Dutch Science Foundation, NWO. 260 k€ Breaking the unbreakable: C-H carbonylation in micro flow and vision to process. Scientific Publications (all are as independent and leading researcher) 101 publications, 14 book chapters, 2 edited books and 1 patent application (To date)
Selected publications 1. A leaf-inspired luminescent solar concentrator for energy efficient continuous-flow photochemistry. Cambie, D.; Zhao, F.; Hessel, V.; Debije, M.G.; Noël, T. Angew. Chem. Int. Ed. 2017, 56, 1050-1054 (selected as VIP paper) 40
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
2. Disulfide-Catalyzed Visible-Light Oxidative Cleavage of C=C Bonds and Evidence of an Olefin-Disulfide Charge-Transfer Complex. Deng, Y.; Wei, X.-J.; Wang, H.; Sun, Y.; Noël, T.; Wang, X. Angew. Chem. Int. Ed. 2017, 56, 832-836. (selected as Hot paper) 3. Practical Photocatalytic Trifluoromethylation and Hydrotrifluoromethylation of Styrenes in Batch and Flow. Straathof, N. J. W.; Cramer, S. E.; Hessel, V.; Noël, T. Angew. Chem. Int. Ed. 2016, 55, 15549-15553. 4. Mild and selective base-free C–H arylation of heteroarenes: Experiment and computation. Gemoets, H. P. L.; Kalvet, I.; Nyuchev, A. V.; Erdmann, N.; Hessel, V.; Schoenebeck, F.; Noël, T. Chem. Sci., 2017, 8, 1046-1055. 5. Applications of continuous-flow photochemistry in organic synthesis, material science and water treatment. Cambié, D.; Bottecchia, C.; Straathof, N. J. W.; Hessel, V.; Noël, T., Chem. Rev., 2016, 116, 10276-10341.
Selected Awards 2016 Thieme Chemistry Journal Award. 2015 VIDI Award (Netherlands Organization for Scientific Research, NWO). 2012 Finalist European Young Chemist Award, EuCheMS Conference. 2011 Incentive Award for Young Researchers (Comité de Gestion du Bulletin des Sociétés Chimiques Belges).
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Visible light photoredox catalysis with radical anions
I. Ghosh, L. Marzo, R. Shaik, A. Das and B. König*
Faculty of Chemistry and Pharmacy, University of Regensburg, Regensburg, Germany *[email protected]
Visible light photocatalysis has made a huge impact on recent developments in chemical synthesis. We have explored over the last two years the use of radical anions as photoactive intermediates in SRN 1 type reactions. An initial photoinduced electron transfer produces a radical anion, which is colored and stable. This is excited again to a transient doublet state that is strongly reducing. Transfer of the excess electron to a substrate, e.g. an aryl halide, initiates the aromatic substitution reaction. Our initial system based on perylenediimide1 suffered from low solubility of the photocatalyst and was improved by using the well-established organic dye rhodamine 6G.2
The reaction principle was established for C-C cross coupling reactions,3 the synthesis of annulated heteroarenes4 and the synthesis of phosphonates.5
Recently, we were able to improve the performance of the reaction further by introducing a sensitization-induced electron transfer instead of direct excitation of the redox active photo- catalysts. This new principle generates highly reactive synthesis intermediates with unprecedented ease from green and blue light.
References
1) I. Ghosh, T. Ghosh, J. I. Bardagi, B. König, Science 2014, 346, 725. 2) I. Ghosh, B. König, Angew. Chem. Int. Ed. 2016, 55, 7676. 3) a) L. Marzo, I. Ghosh, F. Esteban, B. König, ACS Catal. 2016, 6, 6780. B) I. Ghosh, L. Marzo, A. Das, R. Shaikh, B. König, Acc. Chem. Res. 2016, 49, 1566. 4) A. Das, I. Ghosh, B. König, Chem. Commun. 2016, 52, 8695. 5) R. S. Shaikh, S. J. S. Düsel, B. König, ACS Catal. 2016, 6, 8410.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Burkhard König
Institut für Organische Chemie Einhausen 38b Universität Regensburg D-93138 Lappersdorf Universitätsstr. 31 Germany D-93040 Regensburg, Germany phone: +49-941-8703153 phone: +49-941-943-4576/5 mobile: +49-15201678001 fax: +49-941-943-1717 e-mail: [email protected]
Curriculum Vitae
Personal data Date of Birth 23/6/1963 Nationality German martial status married, one child
Education University education in Chemistry
6/96 venia legendi, Habilitation (organic chemistry), Technical University of Braunschweig, Germany 9/91 Ph.D. (Dr. rer. nat) (summa cum laude), University of Hamburg, Germany 9/88 M.S. (Hauptdiplom) (magna cum laude, 1.0), University of Hamburg, Germany 11/85 B.S. (Vordiplom) (magna cum laude, 1.3), University of Hamburg, Germany
Experience 10/99 - present Full professor at the Department of Chemisty, University of Regensburg, Germany. Research areas: Physical-organic chemistry; supramolecular chemistry, photocatalysis, catalytic conversion of renewable resources. 6/93 – 9/99 Research group leader at the Department of Chemistry, Technical University of Braunschweig, Germany. 1/92 - 5/93 Postdoctoral fellow with Prof. Dr. B. M. Trost at Stanford University, U.S.A. 10/91 - 1/92 Visiting research fellow with Prof. Dr. M. A. Bennett at the Research School of Chemistry, Australian National University, Canberra, Australia 3/88 - 9/91 Graduate research with Prof. Dr. A. de Meijere at the University of Hamburg
Awards and activities 43
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
• Editorial board member of “Chemistry – A European Journal” and “European Journal of Organic Chemistry (Chair) (since 2014) • UN-Decade Award on Sustainability 2011/2012 • Dean of the faculty of chemistry since 10/2011 • Literature award of the Fonds of the German Chemical Industry 2007 • Chairman of the Liebig Vereinigung (National organic devision; 2008 – 2012) • Member of the excecutive board of the German Chemical Society (2004 - 2007) • Chairman of the „Arbeitsgemeinschaft Deutscher Universitätsprofessoren Chemie (ADUC) • (2005-2007) • Member of the International Advisory Board of the Institute for Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Prag (since 2004) • Member of the International Advisory Board of the “European Journal of Organic Chemistry” (since 2004) • Invitation fellowship award of the `Japan Society for the Promotion of Science´ (1996) • Award of the Dr. Otto Röhm Gedächnisstiftung (1995) • Fellowship of the Deutsche Forschungsgemeinschaft (Habilitationsstipendium) • Fellowship of the Fonds der Chemischen Industrie (Liebig-Stipendium) • Postdoctoral fellow of the Alexander von Humboldt foundation (Feodor-Lynen fellow) • Graduate fellow of the Studienstiftung des Deutschen Volkes
Publication record Scientific papers and reviews: 314 / H-index 45 books, book reviews, science related articles: 60
Regensburg 11/2016
For additional information, please visit: http://www-oc.chemie.uni-regensburg.de/koenig/index.html
Ten self selected papers
1. Eosin Y Catalyzed Visible Light Oxidative C-C and C-P bond Formation (Times Cited: 238) D. P. Hari, B. Koenig* Org. Lett. 2011, 13, 3852 – 3855. DOI: 10.1021/ol201376v The paper disclosed the first example of using the organic dye eosin Y as visible light photocatalyst; the compound is now widely used by researchers to replace precious Ru(bipy)3Cl2 in synthesis. 2. Metal free, Visible Light Mediated Direct C-H Arylation of Heteroarenes with Aryl Diazonium salts (Times Cited: 200) D. P. Hari, P. Schroll, B. König* J. Am. Chem. Soc. 2012, 134, 2958 – 2961. DOI: 10.1021/ja212099r The Meerwein arylation reaction is known since more than 100 years, but the original protocol using copper salts gives only moderate yields. This has limited the use of the reaction in synthesis. We describe here for the first time the activation of diazonium salts by visible light photoredox catalysis providing a much cleaner reaction and good to excellent product yields. The “Photo Meerwein” reaction has since then been widely applied in organic synthesis.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
3. The Photocatalyzed Meerwein Arylation: Classic Reaction of Aryl Diazonium Salts in a New Light (Times cited: 204) D. P. Hari, B. König* Angew. Chem. Int. Ed. 2013, 52, 4734 – 4743. DOI: 10.1002/anie.201210276 We have summarized the rapid expanding synthetic applications of our „Photo Meerwein“ arylation reaction in this review. 4. Visible Light Photocatalytic Synthesis of Benzothiophenes (Times Cited: 85) D. P. Hari, T. Hering, B. König* Org. Lett. 2012, 14, 5334 – 5337. DOI: 10.1021/ol302517n Application of the „Photo Meerwein“ reaction in the synthesis of important heterocycles. 5. Visible light Promoted Stereoselective Alkylation by Combining Heterogeneous Photocatalysis with Organocatalysis (Times Cited: 85) M. Cherevatskaya, M. Neumann, S. Füldner, C. Harlander, S. Kümmel, S. Dankesreiter, A. Pfitzner, K. Zeitler, B. König* Angew. Chem. Int. Ed. 2012, 51, 4062 – 4066. DOI: 10.1002/anie.201108721 This is the first report combining stereoselective organocatalysis with heterogeneous semiconductor photocatalysis replacing homogeneous photocatalysts, like Ru or Ir complexes by robust and available semiconductors. 6. Reduction of aryl halides by consecutive visible light-induced electron transfer processes (Times Cited: 33) I. Ghosh, T. Ghosh, J. I. Bardagi, B. König* Science 2014, 346, 725-728. This is the first report on consecutive photoinduced electron transfer in visible light photocatalysis. 7. Molecular Imprinting of Luminescent Vesicles (Times Cited: 21) S. Banerjee, B. König* J. Am. Chem. Soc. 2013, 135, 2967 – 2970. DOI: 10.1021/ja4001568 First report of molecular imprinting on the surface of a fluid vesicle giving luminescent nanosensors.
8. Regulation of Human Carbonic Anhydrase I (hCAI) Activity by Using a Photochromic Inhibitor (Times Cited: 50) D. Vomasta, C. Högner, N. R. Branda,* B. König* Angew. Chem. Int. Ed. 2008, 47, 7644 - 7647. DOI: 10.1002/anie.200802242 Photochromic enzyme inhibitor based on a dithienylethene chromophore allows the reversible light controlled inhibition of an enzyme.
9. Potent and selective inhibitors of breast cancer resistance protein (ABCG2) derived from the p- glycoprotein (ABCB1) modulator tariquidar (Times Cited: 62) M. Kühnle, M. Egger, C. Müller, A. Mahringer, G. Bernhardt, G. Fricker, B. König,* A. Buschauer* J. Med. Chem. 2009, 52, 1190 – 1197. DOI: 10.1021/jm8013822 The compound with currently highest potency and selectivity for ABCG2 inhibition is reported. 10. Conversion of carbohydrates into 5-hydroxymethylfurfural in highly concentrated low melting mixtures (Times Cited: 91) F. Ilgen, D. Ott, D. Kralisch, C. Reil, A. Palmberger, B. König* Green Chem. 2009, 11, 1948 – 1954. DOI: 10.1039/b917548m First report of the efficient and solvent-free conversion of carbohydrates into HMF using a low melting mixture.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
New photoredox-induced cascade reactions
Malte Brasholza,*
aUniversity of Hamburg, Department of Chemistry – Institute of Organic Chemistry, Hamburg, Germany [email protected] Photoredox-mediated one-electron reduction of organic halides is a mild and efficient method to generate the corresponding carbon-centered radicals. While the reduction of activated acyl halides can readily be accomplished using common ruthenium(II) polypyridyl photocatalysts, unactivated alkyl, alkenyl and aryl halides require more strongly reducing conditions, and in particular iridium(III) polyheteroaryl complexes possess suitable redox potentials to bring about these more challenging reductive transformations.1 Photoinduced free radical additions have been utilized extensively in the synthesis of functionalized heterocycles, however, mostly giving aromatic products. We developed dearomative radical additions onto indoles, and an iridium(III)-catalyzed reductive radical (4+2)- cyclization between N-iodoethylindoles and alkenes led to valuable tricyclic benzindolizidine products.2 Further extension of our methodology enabled a new stereoselective synthesis of functionalized hexahydrocarbazoles, based on an unprecedented dearomative radical (4+2)- cyclization/1,4-addition cascade between 3-(2-iodoethyl)indoles and acceptor-substituted alkenes. The photoredox-induced cascade reaction simultaneously generated three C-C and one C-H bonds, along with three contiguous stereogenic centers.3
dearomative radical (4+2)-cyclization (4+2)-cyclization / 1,4-addition cascade
Mechanistic aspects of these dearomative radical cyclizations of indole derivatives will be discussed, as well as synthetic applications of the heterocyclic products, which are highly valuable intermediates for the synthesis of novel antibiotics as well as unnatural ring homologs of polycyclic indoline alkaloids.
References [1] Reviews: (a) C. K. Prier, D. A. Rankic, D. W. C. Mac Millan, Chem. Rev. 2013, 113, 5322-5363. (b) D. Ravelli, S. Protti, M. Fagnoni, Chem. Rev. 2016, 116, 9850-9913. [2] S. Mühmel, D. Alpers, F. Hoffmann, M. Brasholz, Chem. Eur. J. 2015, 21, 12308-12312.
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[3] D. Alpers, M. Gallhof, J. Witt, F. Hoffmann, M. Brasholz, Angew. Chem. 2017, 129, 1423-1427; Angew. Chem. Int. Ed. 2017, 56, 1402-1406.
Malte Brasholz studied Chemistry at Freie Universität Berlin and obtained his PhD from the same institution in 2007, under the guidance of Prof. Hans-Ulrich Reissig. A short-term stay in the laboratory of Prof. Hisashi Yamamoto at the University of Chicago in 2008 was followed by one year of postdoctoral research in the group of Prof. Steven V. Ley at the University of Cambridge. A second year of postdoctoral studies led Malte to Australia, where he worked at CSIRO Molecular and Health Technologies in association with Prof. Andrew B. Holmes at the University of Melbourne. In 2010, he was appointed Research Scientist at CSIRO Materials Science and Engineering. From April 2012, Malte established an independent research group at the Institute of Chemistry at the University of Hamburg.
Academic CV
. 2012 Assistant Professor of Organic Chemistry, University of Hamburg 2010 Research Scientist, CSIRO Materials Science and Engineering, Melbourne Postdoctoral fellow, CSIRO Molecular and Health Technologies 2009 and group of Prof. Andrew B. Holmes, University of Melbourne 2008 Postdoctoral fellow, group of Prof. Steven V. Ley, University of Cambridge 2007 Short-term scholar, group of Prof. Hisashi Yamamoto, University of Chicago 2007 PhD in Chemistry, group of Prof. Hans-Ulrich Reissig, Freie Universität Berlin 2004 Diplom degree in Chemistry, group of Prof. Hans-Ulrich Reissig, Freie Universität Berlin
Awards and Fellowships:
. 2016 GIAN lectureship, Government of India 2015 Donation by Dr. Otto Röhm Gedächtnisstiftung 2014 Thieme Journal Award 2009 Postdoctoral fellowship, CSIRO Office of the CEO Awards Scheme 2008 Postdoctoral fellowship, Deutsche Forschungsgemeinschaft (DFG) 2005 PhD fellowship, Fonds der Chemischen Industrie (FCI)
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Photoinduced Electron Transfer in Base-promoted Homolytic Aromatic Substitution and Related Systems. Is t-butoxide anion a key ingredient?
M. E. Budén;a J. F. Guastavino,a J. I. Bardagí, a Marcelo Puiatti a and R. A. Rossia*
a Instituto de Investigaciones en Físicoquímica de Córdoba, INFIQC, Córdoba, Argentina *[email protected]
In the recent years, there is a booming of research in transition metal-free couplings of ArX to arenes to form biaryls (eq 1). These reactions are triggered by alkali metal tert-butoxides in the presence of various additives via Base-promoted Homolytic Aromatic Substitution (BHAS).1,2 In 2008, the original report presented by Itami showed that KOtBu promoted the arylation of pyrazine and other electron‐poor arenes from ArI or ArBr, under elevated temperatures or MW irradiation.3 Later, different research groups have reported the construction of biaryls and stilbene derivatives from unactivated aromatic compounds by direct C-H activation of benzene or styrene using NaOtBu or KOtBu in the presence of a range of organic additives as ligands.2 As a consequence, the role of these organic additives in radical initiation attracted much research interest and different mechanisms have been proposed.4
Previously we reported on photoredox reactions for synthesis of biaryls (BHAS) and styrenes (Mizoroki−Heck-type) as a new alternative to induce these transformations at room temperature (eqs 1 and 2).5 Now, we propose a new alternative to induce these photoreactions, that involves dimsyl anion as a key ingredient. However, C-H functionalization of alkenes is produce without any solvent. Computational studies were performed to help to understand the initiation steps of these processes.
1. Studer, A.; Curran, D. P. Angew. Chemie Int. Ed. 2011, 50, 5018–5022. 2. a) Sun, C.; Shi, Z. Chem. Rev. 2014, 114, 9219–9280. b) Hussain, I.; Singh, T. Adv. Synth. Catal. 2014, 356, 1661– 1696. c) Mehta, V. P.; Punji, B. RSC Adv. 2013, 3, 11957 and references cited herein. 3. Yanagisawa, S.; Ueda, K.; Taniguchi, T.; Itami, K. Org. Lett. 2008, 10, 4673–4676. 4. a) Zhou, S.; Anderson, G. M.; Mondal, B.; Doni, E.; Ironmonger, V.; Kranz, M.; Tuttle, T.; Murphy, J. A. Chem. Sci. 2014, 5, 476–482. b) Zhou, S.; Doni, E.; Anderson, G. M.; Kane, R. G.; MacDougall, S. W.; Ironmonger, V. M.; Tuttle, T.; Murphy, J. A. J. Am. Chem. Soc. 2014, 136, 17818–17826. c) Patil, M. J. Org. Chem. 2016, 81, 632–639. 5. a) Budén, M. E.; Guastavino, J. F.; Rossi, R. A. Org. Lett. 2013, 15, 1174–1177. b) Guastavino, J. F.; Budén, M. E.; Rossi, R. A. J. Org. Chem. 2014, 79, 9104–9111. 48
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
María Eugenia Budén
Address Ernesto La Padula 865. (CP 5000), Cordoba, Argentine Telephone (+54) 0351 460 2736 Nationality Argentine Date of birth 13th of August 1981 e-mail [email protected]
CURRENT RESEARCH POSITION
From April 2013 Assistant researcher at CONICET. Title: Photoinduced Direct C-H-Arylation via Base-Promoted Homolytic Aromatic Substitution
FELLOWSHIP AWARDS
From April 2010 to March 2012 Postdoctoral Research Fellowship from the National Research Council of Argentina. Title: Synthesis of Biaryls and Heterocycles by Metal-Catalyzed Organic Reactions and SRN1. Research Advisor: Dr. Roberto A. Rossi and Sandra E. Martin From April 2005 to March 2010 Doctoral Research Fellowship from the National Research Council of Argentina. Thesis Title: New Tandem Reactions by SRN1 Mechanisms. Research Advisor: Dr. Roberto A. Rossi.
RESEARCH INTERESTS
Organic synthesis and photochemistry – Radical chemistry – Redox processes in organic syntheses – Heterocyclic chemistry-.
SCIENTIFIC PUBLICATIONS
13 papers, 5 chapter of books and 22 oral and poster presentations.
STAYS IN INTERNATIONALLY RECOGNIZED CENTRES
From April 2011 to October 2011 Laboratori de Química Farmacèutica (Unitat Associada al CSIC), Facultat de Farmàcia, Universitat de Barcelona, Barcelona, Spain. Topic: Tetrasubstituted alkenes by metathesis of 1,1-disubstituted alkenes: potential application for the synthesis of belt compounds Research Advisor: Dr. Pelayo Camps
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
KOtBu promoted intermolecular cross-coupling through electron transfer
A. Tlili,a,* J. Bergèsb and M. Tailleferb,*
aICBMS - SURCOOF (UMR CNRS 5246 - Lyon), Villeurbanne, France bENSCM - UMR 5253 - Institut Charles Gerhardt, Montpellier, France (Times New Roman, italicized in 10 pt.) *[email protected]
The talk will mainly focus on our recent ongoing research program based on transition metal free cross-coupling reactions. Indeed, we recently developed a Matsuda-Heck coupling reaction allowing the formation of stilbenes derivatives using arenediazonium salts and styrene derivatives as coupling partners. Theses reactions proceed under transition metal and irradiation-free conditions.1
+ - N2 BF4 KOtBu R' R + R' R
1.J. Bergès, A. Tlili, M. Taillefer, manuscript in preparation
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Anis TLILI [email protected] ICBMS-SURCOOF + 33 4 72 44 85 28 Université Claude Bernard - Lyon 1 43 Bd du 11 novembre 1918 Bat. Raulin (4ème étage) 69622 Villeurbanne Cedex – France Date of birth: February 25, 1983, Married
CNRS Research Fellow
Experience
10/2014- CNRS Research Fellow To date ICBMS - SURCOOF (UMR CNRS 5246 - Lyon), Université Claude Bernard - Lyon 1.
09/2013- Chercheur postdoctoral, CEA - Commissariat à l'énergie atomique -Saclay, France. 08/2014 Synthesis of new phosphine based frustrated Lewis pair for the reduction of CO2. In collaboration with the group of: Dr. A. Marinetti
01/2012- Chercheur postdoctoral, Leibniz-Institut für Katalyse, Allemagne, Prof. M. Beller. 08/2013 Transition metals catalyzed reactions under carbon monoxide.
2011 Internship (2 months), ENS Paris, France, Supervised by Dr. A. Jutand. Electrochemical studies on Cu-catalyzed C-N and C-O Bond formating reactions
2008-2011 Thèse en chimie, ENSC Montpellier, France, Dr. M. Taillefer. Cu -catalyzed C-C, C-N and C-O Bond formating reactions.
2007-2008 Master internship (6 mois), Université de Bourgogne, Dijon, France, Prof. S. Jugé. New P-Chirogenic diphosphine complexes.
PUBLICATIONS AND PATENTS
33 publications & patents 2 book chapters
Awards
First Price IDEAS COMPETITION “CATALYSIS 2020“, Leibniz-Institut für Katalyse Awarded Leibniz grant for Post-doctoral researcher (01/2012-08/2013), Leibniz-Institut für Katalyse Solvias AG lecture 2016 51
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
“The Palme d’Or goes to …”. A search for the best functional for dealing with anionic organic species
M. Puiatti;a,* J. L. Borioni;b D. M. A. Vera b and A. B. Pierinia,
aINFIQC- Instituto de Investigaciones en Físicoquímica de Córdoba, Córdoba, Argentina b Dpto. Química, Fac. Cs. Exactas y Naturales, Universidad Nacional de Mar del Plata, Mar del Plata, Argentina * [email protected] During the last few decades, density functional theory (DFT) has become the method of choice in quantum chemical studies. Indeed, many experimental investigations routinely include such calculations, using a popular code, a standard basis, and a standard functional approximation.1 It is well known that DFT has provided approximations that work quite well for some problems and fail for others.2 Hence, a proper recommendation should be to search for the DFT functional that works better within the problem to be studied. In the present study we addressed the overall performance of 23 different DFT functionals and ab initio methods for studying anionic organic species. In order to evaluate its scope and limitations, electron affinities (EA) and reduction potentials 0 (퐸푅푒푑) were computed. A set of 60 molecules was employed for the calculation of EAs, in the range 0 of 0 to -3.4 eV. Besides, 62 compounds were selected for the computation of the 퐸푅푒푑, with potentials, measured in acetonitrile, from -2.71 V to 0.06 V (vs. standard hydrogen electrode, SHE). For compounds with negative EAs, hybrid GGA gave better results than pure and meta GGA double hybrid functionals and ab initio methods yield poorly with MADs higher than 0.5 eV. 0 The calculations of 퐸푅푒푑 are strongly dependent on the quality of the solvation energies of the 0 charged species. This was evidenced in the correlation of calculated absolute 퐸푅푒푑 vs. experimental 0 퐸푅푒푑. However, there is a significant improvement after the use of a proper redox partner. The best results were obtained with hybrid GGA functionals, B3PW91 and PBE0. TPSSh and M06 were the better meta GGA. Pure GGA functionals gave good results, with low dispersion, but high MADs, that could improve by choosing a proper reference.
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The ideal scenario should give a podium with some functionals that outperform the others. However, there is a suitable DFT functional for each problem instead of a universal one that could solve almost all the situations within different conditions. References: 1- Burke, K., J Chem Phys, 2012, 136, 150901. 2- Medvedev, M. G.; Bushmarinov, I. S.; Sun, J.; Perdew, J. P.; Lyssenko, K. A. Science, 2017, 355, 49-52.
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MARCELO PUIATTI Nationality: Argentine Date of Birth: 10th of February 1977 Address: Arq. Ernesto La Padula 865. Ba: Parque Vélez Sarsfield. Córdoba. Argentina. Telephone: +54-351-156742579 Email: [email protected] [email protected]
CURRENT POSITION
From Assistant Profesor. Facultad de Ciencias Químicas. Universidad Nacional de 2004 Córdoba. Researcher. INFIQC. CONICET. “Application of Molecular Modeling to the From Study of Organic and Bio-organic Systems”. Former Director: Prof. Dra. Adriana 2009 B. Pierini RESEARCH INTEREST Electron Transfer Reactions; Radical Anions; DFT; Photochemistry; AChE Inhibitors; Molecular Modeling SCIENTIFIC PUBLICATIONS 11 Scientific Articles, 25 Presentations to Workshops and Scientific Meetings, 3 Invited Conferences.
MOST RELEVANT ARTICLES
“In search of the best DFT functional for dealing with organic anionic species”. José L. Borioni, Marcelo Puiatti, D. Mariano A. Vera and Adriana B. Pierini. Phys. Chem. Chem. Phys. Accepted. doi: 10.1039/C6CP06163J. “In search for an optimal methodology to calculate the valence electron affinities of temporary anions.” Puiatti, M.; Vera, D.M.A; Pierini, A. B.. Phys. Chem. Chem. Phys., 2009, 11, 9013 - 9024. “Species with negative electron affinity and standard DFT methods. Finding the valence anions” Marcelo Puiatti, D. Mariano A. Vera, Adriana B. Pierini. Phys. Chem. Chem. Phys., 2008, 10,1374-1379. FORMATION
2006. PhD. Doctor en Ciencias Químicas. “Study of Electron Transfer Oxidation Reactions”. Advisor: Dra. Alicia B. PEÑÉÑORY. Fac. de Cs. Químicas. Universidad Nacional de Córdoba.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
2006-2009 Post-doctoral Position. “Computational Chemistry Applied to Study of Intermediate Species of Electron Transfer Reactions”. Director: Dra. Adriana B. Pierini. Fac. Ciencias Químicas. Universidad Nacional de Córdoba. Post-doctoral Fellowship CONICET. 2011-2012 Post-doctoral Position. Life Sciencies Department BSC Barcelona. “Electronic and Atomic Protein Modeling”. Director: Dr. Víctor Guallar. 01/02/2011 hasta 28/02/2012. MAE Fellowship Spain.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Characterization of single electron transfer steps in water oxidation through DFT calculations
Feliu Maseras
a Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science of Technology, Av. Països Catalans 16, 43007 Tarragona, Catalonia, Spain (Times New Roman, italicized in 10 pt.) bDepartament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia, Spain * [email protected] Computational homogeneous catalysis has been traditionally dominated by two-electron transfer processes.1 The increasing interest in the catalytic processes involving first row transtion metals has lead to the identification of a number of processes where single electron transfer processes play a critical role.2-6 In this presentation we will discuss some of our recent contributions in the field, with a special focus on copper-catalyzed O-O water oxidation3,6 (see Figure). Calculations demonstrate that single electron transfer processes replace in some cases the two-electron transfer water nucleophilic attack mechanism, the main operating mode for second- and third-row transition metals.
References (Times New Roman, 10 pt.), denoted by superscript numbers in the text, it should be listed at the end of the text using ACS format. 1. Sameera, W. M. C.; Maseras, F. WIREs Comp. Mol. Sci. 2012, 2, 375-385. 2. Jover, J.; Spuhler, P.; Zhao, L. G.; McArdle, C. Catal. Sci. Tech. 2014, 4, 4200- 4209. 3. Garrido-Barros, P.; Funes-Ardoiz, I.; Drouet, S.; Benet-Buchholz, J.; Maseras, F.; Llobet, A. J. Am. Chem. Soc. 2015, 137, 6758-6761. 4. Fernandez-Alvarez, V. M.; Nappi, M.; Melchiorre, P.; Maseras, F. Org. Lett. 2015, 17, 2676-26795. 5. Funes-Ardoiz, I.; Maseras, F. Angew. Chem. Int. Ed. 2016, 55, 2764-2767. 6. Funes-Ardoiz, I.; Garrido-Barros, P.; Llobet, A.; Maseras, F. ACS Catal. 2017, DOI:10.1021/acscatal.6b03253 56
ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Feliu Maseras
Contact information [email protected] Experience Research group leader in Institute of Chemical Research of Catalonia (ICIQ) since 2004 Assoc Prof in Universitat Autònoma de Barcelona since 1998 Assoc Researcher in Montpellier 1996-98 Post-doctoral researcher in Okazaki 1992-94 Education PhD in Chemistry, Universitat Autònoma de Barcelona, 1991 Research topics Research interest focused in the design an application of QM/MM methods to problems of practical interest and the computational study of the reactivity of molecular systems containing transition metal atoms.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Charge Transfer Processes : Prime Role of Optimized Molecular Orbitals
V. Roberta,*, A. Domingoa, T. Kraha and B. Meyera
aLaboratoire de Chimie Quantique, CNRS Université de Strasbourg, Strasbourg, France *[email protected]
abstract : The key role played by the molecular orbitals in describing electron transfer processes is examined in mixed-valence compounds (see Figure, Fe3+/Fe2+ biomimetic non-heme1) and analogues. It is suggested that the extent of electronic reorganization induced by intervalence charge transfer can reach up to several electron-volts2,3. By means of ab initio calculations (wave-function type, CASSCF/CASPT2), it is shown that the energetic profile shows strong similarities to the Marcus’s theory. Such observation questions the standard quantum chemistry approaches used to describe internal electron transfer phenomena in molecular science devices.
References: 1. Balasubramanian, R.; Blondin, G.; Canales, J. C.; Costentin, C.; Latour, J.-M.; Robert, M.; Savéant, J.-M. J Am. Chem. Soc. 2012, 134, 1906. 2. Domingo, A.; Angeli, C.; de Graaf, C.; Robert, V. J. Comp. Chem. 2015, 36, 861. 3. Meyer, B. Domingo, A.; Krah, T.; Robert, V. Dalton. Trans. 2014, 43, 11209.
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Vincent ROBERT Date of birth: March 17th 1969 E-mail: [email protected] - webpage: http://quantique.u-strasbg.fr/pperso/vincent/
CURRENT POSITION
Full Professor Strasbourg University, Laboratoire de Chimie Quantique Director of Laboratoire de Chimie Quantique, Strasbourg Director of Réseau Chimie Théorique Français Grand-Est Member of LabEx Complex Systems, Strasbourg University Coordination Leader ANR French Research Project (2007-2010) Supervisor 1 PhD, 1 PostDoc
SCIENTIFIC BACKGROUND 2010-present Full Professor (section 31), Strasbourg University 1997-2010 Assistant Professeur, Physical Chemistry, Lyon 1 University 2001-2003 Sabbatical CNRS, Laboratoire de Chimie et Physique Quantiques, Toulouse
SCIENTIFIC ACTIVITIES semi empirical calculations, ab initio, methodology - spectroscopies, magnetic systems, macroscopic properties, spintronics
Publication (98) 62 ACS, APS Journals and 36 in Eur. Journals 2 reviews, 2 book chapters, 3 cover pages
Invited Professor Nagoya University, Japan, September 2007, 2009, 2012 Tarragona University, Spain, April-May 2008
Conferences 20 invited conferences, 30 invited seminars
5 Reference Publications
1. Mizumo, A.; Shuku, Y.; Suizu, R.; Matsushita, M.; Tsuchiizu, M.; Reta Maneru, D.; Illas, F.; Robert, V.; Awaga, K. J. Am. Chem. Soc. 2015, 137, 7612 2. Domingo, A.; de Graaf, C.; Angeli, C.; Robert, V. J. Comp. Chem. 2015, 36, 861 3. Krah, T.; Ben Amor, N.; Maynau, D.; Berger, J.A.; Robert, V. J. Mol. Mod. 2014, 20, 2240 4. Vérot, M.; Borshch, S.A.; Robert, V. J. Chem. Phys. 2013, 138, 094105 5. Perraud, O.; Robert, V.; Gornitzka, H.; Martinez, A.; Dutasta, J.P. Angew. Chem. Int. Ed. 2012, 51, 504
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ETRADCHEM Workshop 2017 23rd-24th March 2017. Villeurbanne, France
Exploring the reactivity of the Kagan’s reagent from a theoretical perspective
L. Perrin;a,* X. Zhaob and L. Maronb
aUniversité Lyon 1, CNRS, INSA, CPE, UMR 5246, ICBMS, ITEMM, 43 Bd du 11 novembre 1918, 69622 Villeurbanne cedex, France b LPCNO, Université de Toulouse, INSA, UPS, CNRS, 135 avenue de Rangueil, F-31077 Toulouse, France *[email protected]
The Kagan’s reagent (SmI2) is one of the most versatile single-electron reducing agent in organic synthesis. Since its seminal report,1 the scope off application of this reagent has been largely enriched by adjusting the reaction conditions and especially the proper solvent / co-solvent(s) combinations.2 Modeling single electron transfer mediated by f-element proved to be inaccessible until recently.3 This contribution details the modeling strategy developed for the modeling of the reactivity SmI2 in complex environments and addresses how co-solvents such as HMPA, water and amine not only modify the reducing power of SmI2 but also strongly affect reaction mechanisms. More precisely, our pioneering mechanistic investigation addresses the mechanism by which alkyl- halides and various carbonyl derivatives are selectively reduced by SmI2 depending on the reaction conditions.4 A particular emphasis will be laid on the role played by bimetallic intermediates and subsequent Bimetallic Proton Coupled Electron Transfer (BPCET).
FIG. Bimetallic reduction of aliphatic esters by SmI2 in ternary THF/water/amine
Namy, J. L.; Girard, P.; Kagan, H. B. Nouv. J. Chim. 1977, 1, 5; Girard, P.; Namy, J. L.; Kagan, H. B. J. Am. Chem. Soc. 1980, 102, 2693. Procter, D. J.; Flowers, R. A., II; Skrydstrup, T. Organic Synthesis Using Samarium Diiodide: A Practical Guide; RSC Publishing: Cambridge, 2010; Szostak, M.; Procter, D. J. Angew. Chem., Int. Ed. 2011, 50, 7737. Szostak, M.; Spain, M.; Procter, D. J. Chem. Soc. Rev. 2013, 42, 9155. Kefalidis, C. E.; Essafi, S.; Perrin, L.; Maron, L. Inorg. Chem. 2014, 53, 3427. Kefalidis, C. E.; Perrin, L.; Maron, L. Eur. J. Inorg. Chem. 2013, 22-23, 4041 and unpublished results.
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Lionel Perrin received his Ph.D. in 2004 from Université Montpellier (Odile Eisenstein and Laurent Maron directors) and joined the CNRS in 2005. Since 2013, he is group leader of Interface Theory Experiment: Mechanism and Modeling (ITEMM) at Université Lyon 1, he focuses on the interplay between experiments and theory for polymerization and multistep organic reactions catalyzed by organometallic species.
Curriculum 2016 « Habilitation à Diriger des Recherches » Université Lyon 1 2004-2005 CNRS Post-doctoral fellow, CEA-Saclay 2001-2004 PhD of Theoretical Physiocal-Chemistry Université Montpellier II 2000-2001 Master of Theoretical Physiocal-Chemistry Université Toulouse III 1997-2000 Ingénieur Chimiste Ecole Supérieure de Chimie Organique et Minérale ESCOM
Lab Experiences 2013- Chargé de recherche au CNRS (UMR 5246, ICBMS), Univ-Lyon 1 ITEMM Group leader Theoretical/experiment interface, molecular modeling and reaction mechanism exploration. Folding and self-assembly mechanism. 2008-2013 Chargé de recherche au CNRS (UMR 5215, LPCNO), INSA-Toulouse Computational chemistry applied to organometallic and bio-inorganic chemistry 2005-2008 Chargé de recherche au CNRS (URA 2096, PMTE), CEA-Saclay Modeling of the dynamics and reactivities of metalloproteins 2004-2005 Post-doctoral fellow at CEA-Saclay, F. André et M. Delaforge (CNRS valorisation / Servier) Computational investigation of recognition mechanism of P450s 2001-2004 Thèse de doctorat à l’Université Montpellier II, O.Eisenstein et L.Maron (Michelin, CIFRE) Theoretical investigation of the structure and reactivity of organolanthanide complexes
Major Collaborators R.A. Andersen UC-Berkeley, USA C. Boisson CPE-Lyon I. Marek Technion Haifa, Israël M. Taoufik CPE-Lyon D.J. Procter University of Manchester, UK C. Taillefumier Université Clermond-Ferrand S. Maeda Hokkaido University, Japon O. Eisenstein Université Montpellier II K. Morokuma FIFC-Kyoto, Japon Manufacture MICHELIN
Recent publications Deciphering selectivity in organic reactions: A multifaceted problem. Balcells D, Clot E, Eisenstein O, Nova A, Perrin L: Acc. Chem. Res. 49:1070-1078, 2016 Spécial Issue on Computational Catalysis for Organic Synthesis Preparation and Reactivity of Acyclic Chiral Allylzinc Species via a Zn-Brook Rearrangement. Leibeling M, Shurrush KA, Perrin L, Marek I: Angew. Chem. Int. Ed. 55:6057-6061, 2016 Weak backbone CH…O=C and side chain tBu…tBu London interactions help promote helix folding of achiral NtBu peptoids. Angelici G, Bhattacharjee N, Roy O, Faure S, Didierjean C, Jolibois F, Perrin L*, Taillefumier: Chem. Commun. 52:4573-4576, 2016 New perspectives in organolanthanide chemistry from redox to bond metathesis: Insights from theory. Kefalidis CE, Castro L, Perrin L, Del Rosal I, Maron L: Chem. Soc. Rev. 45:2516-2543, 2016. Ethylene-Butadiene Copolymerization by Neodymocene complexes: a Ligand Structure / Activity / Polymer Microstructure Relationship based on DFT calculations. Nsiri H, Belaid I, Larini P, Thuilliez J, Boisson C, Perrin L*: ACS Catal. 6:1028-1036, 2016.