Book of Abstracts
2
Tehran Time Montpellier time Speaker page
12:00-12:30 09:30-10:00 "Saeed Balalaie" Professor 4
12:30-13:00 10:00-10:30 "David Virieux" Professor 5
13:00-13:30 10:30-11:00 "Babak Kaboudin" Professor 6
13:30-14:00 11:00-11:20 "Camille Oger" Associate Professor 7
14:00-14:10 11:20-11:30 "Mina Hariri " Doctor 8
14:10-15:30 11:30-13:00 Lunch
15:30-15:50 13:00-13:20 "Vahid Khakyzadeh" Assistant Professor 9
15:50-16:10 13:20-13:40 "Florian Jaroschik" Researcher 10
16:10-16:30 13:40-14:00 " Fereshteh Ahmadi" Assistant Professor 11 16:30-16:50 14:00-14:20 "Lubomir Vezenkov" Associate Professor 12
16:50-17:10 14:20-14:40 "Tahar Ayad" Associate Professor 13
17:10-17:20 14:40-14:50 "Lucas Mele" Ph.D.
Table of Contents
Functionalized Oximes: A multi-purpose building block for the generation of N-heterocycles ... 3 Saeed Balalaie Professor
Learning From Fails, Relevant Successes in Drug Discovery of Phosphorus-Based Neutral Heterocycles ... 4 David Virieux Professor
Two decades of research on the synthesis of organophosphorous compounds from dialkyl phosphites ... 5 Babak Kaboudin Professor
Total synthesis, a keystone for the discovery of bioactive molecules. Example of polyunsaturated fatty acid
metabolites. ... 6 Camille Oger Associate Professor
Design, Synthesis and Application of a new family of compounds Isophosphinoline 2-oxides ... 7 Mina Hariri Doctor
Design a New Silver Protofilament Frameworks (SPFs) as Heterogeneous Catalyst for Coupling Reactions ... 8 Vahid Khakyzadeh Assistant Professor
Lanthanide-mediated C-F bond activation : tuning the regioselectivity in the reaction of -difluorinated metal- pentadienyl complexes with aldehydes ... 9 Florian Jaroschik Researcher
An Overview of Isocyanide Insertion Reactions, Focusing on Isocyanide Insertion-Cyclization Reactions ... 10 Fereshteh Ahmadi Assistant Professor
Multi-Lactamization Reaction for the Conception of Foldamers and Cell Penetrating Vectors ... 11 Lubomir Vezenkov Associate Professor
Chiral diphenylphosphine dioxides bearing a bis(triazolyl) backbone as promising Lewis bases for asymmetric
organocatalysis ... 12 Tahar Ayad Associate Professor
From strained phosphine oxide to original atropochiral ligand: an ImperialPhos story ... 13 Lucas Mele Ph.D.
3
Functionalized Oximes: A multi-purpose building block for the generation of N- heterocycles
Saeed Balalaie
11. Peptide Chemistry Research Center, K. N. Toosi University of Technology, P. O. Box 15875-4416, Tehran, IRAN, E-mail: [email protected]
Abstract – The synthesis of complex molecules and heterocyclic backbones using simple starting materials, is an interesting subject in organic synthesis. In this talk, recent results about the use of 2-alkynylbenzaldoximes and
functionalized oximes and their application for the synthesis of starting will be discussed.
Кеуwords – 2-alkynylbenzaldoximes, Cyclization, Multicomponent Reactions, High Bond-Forming Efficiency.
References
[1] Hayatgheybi, S.; Khosravi, H.; Zahedian Tejeneki, H.; Balalaie, S.; Synthesis of N-(Isoquinolin-1-yl)sulfonamides via Ag2O-catalyzed Tandem Reaction of ortho-Alkynylbenzaldoximes with Bench-top Stabilized Ketenimines.
Org. Lett. 2021, 23, 3524-3529.
[2] Nikbakht, A.; Amiri, K.; Khosravi, H.; Zhou, Y.; Balalaie, S.; Breit, B. Copper-Catalyzed Cycloisomerization of Unactivated Allene-Tethered O-Propargyl Oximes: A Domino Reaction Sequence toward the Synthesis of Hexahydropyrrolo[3,4-b]azepin-5(4H)-ones Org. Lett. 2021, 23, 3343-3348.
Curriculum Vitae : Saeed Balalaie is Professor of organic chemistry at K. N. Toosi University of Technology. He studied chemistry in Tehran University, Shahid Beheshti and Sharif University of Technology for his BSc, MSc. and his PhD. His doctoral dissertation was about Photooxygenation of organic compounds under supervision of Prof. M. M. Hashemi and Prof. J. Ipaktschi on Dec. 1996.
From 2001-2003 he received Alexander von Humboldt research fellowship and he carried out research work in University of Heidelberg with Prof. Rolf Gleiter. He received more time short research stay award from Alexander von Humboldt Foundation. He started his work in K. N. Toosi University of Technology on Feb. 1997 as assistant professor and qualified on 2003 and 2007 as associate and full professor. His interest is designing of novel metal- catalyzed sequential reactions, peptide chemistry and synthesis of API.
4
Learning From Fails, Relevant Successes in Drug Discovery of Phosphorus-Based Neutral Heterocycles
David Virieux
11 ICGM, Univ. Montpellier, ENSCM, CNRS, Montpellier, FRANCE - E-mail: [email protected]
Abstract – Phosphorus element is one of the essential building blocks of life. While phosphates predominate and modulate essential functions of all living organisms, the few natural phosphorus molecules yet discovered suggest a much broader spectrum of activity.[1] However, the wide reactivity associated to this element suggests that there is much more than what living organisms have already synthesized. In particular, uncharged phosphorus compounds, namely, phosphine oxides, neutral phosphonates and phosphinates, have been largely neglected opening uncovered areas of chemical space.[2] Our group has been exploring several families of phosphorus heterocycles with applications as agrochemicals or as pharmaceuticals.[3] After detailing approaches on potential inhibitors of the non-mevalonate pathway for the biosynthesis of isoprenoid precursors, we will present other series of bioactives molecules.[4]
Кеуwords – Phosphorus heterocycles, bioactive molecules.
References
[1] Metcalf, W. W.; van der Donk, W. A. Annu. Rev. Biochem. 2009, 78, 65–94.
[2] Smith, B. R.; Eastman, C. M.; Njardarson, J. T. J. Med. Chem. 2014, 57, 9764–9773.
[3] Volle, J.-N.; Guillon, R.; Bancel, F.; Bekro, Y.-A.; Pirat, J.-L.; Virieux, D. In Advances in Heterocyclic Chemistry;
2016; Vol. 118, pp 129–193.
[4] Maurice, T.; Volle, J.-N.; Strehaiano, M.; Crouzier, L.; Pereira, C.; Kaloyanov, N.; Virieux, D.; Pirat, J.-L. Pharmacol.
Res. 2019, 144, 315–330.
Curriculum Vitae : Prof. Virieux graduated from the National Graduate School of Chemistry of Montpellier in 1993. He was introduced to Organic Chemistry as graduate chemist in the laboratory of Professor Henri-Jean CRISTAU from 1994 to 1998 where he received his PhD from the University of Montpellier. He moved in 1998 to the USA as postdoctoral researcher. He performed hit to lead discovery for Rhône-Poulenc Ag Co in North Carolina. Virieux began his independent academic career at ENSCM, where he was Assistant professor (1999) and then Full Professor (2007). Since 2007, he is Chair of the Department of Organic Chemistry at ENSCM.
Professor Virieux is a synthetic organic chemist with a strong commitment in organic synthesis and organophosphorus chemistry. Characterised by a unifying focus to exploit chemical approaches for practical developments in Medicine or Agrochemistry, he identified and generated biomolecules from hits to leads for several pharmaceutical applications. This synthetic chemistry effort led to the design of tailored synthetic drug candidates, that make a therapeutic difference in areas of unmet medical need.
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Two decades of research on the synthesis of organophosphorous compounds from dialkyl phosphites
Babak Kaboudin
11. Department of Chemistry, Institute for Advanced Studies in Basic Sciences, IRAN, Zanjan, No.444, Prof. Yousef Sobouti Blvd., 45137-66731, E-mail: [email protected]
Abstract – Dialkyl phosphites have been proven to be a valuable reagent for the synthesis of various classes of organophosphorus molecules in academic, biological and industrial research. Synthetic uses of dialkyl phosphites in P-C and P-heteroatom bond forming reactions with aldehydes, imines, nitriles, and thiols are discussed.
Кеуwords– Dialkyl phosphite, Aminophosphonates, Aminobisphosphonates, Thiophosphates, Hydroxyphosphonates, P-S Coupling, P-C Formation
H P O
OEt OEt P
O OEt OEt N R
R P
O OEt OEt H2N
R
P O
OEt OEt HN
R P
O OEtOEt HO
R
S P O
OEtOEt
NH4 S P
O OEt OEt R
R' P
O OEtOEt N R
P R
HN R
P O O
OEt EtO
OEt EtO
R
R' O
P O
OEtOEt O R O
O R
S R
O P S
OEt OEt O
RX O R Cl
N NH
CO2H
R P O
OEt OEt RSH
S P O
OEt OEt R
R C N RCHO NH3
RCHO
RCHO R'NH2
R'NH2
RCHO AC2O
AC2O
S8, NH3 H+
H P O
OEt OEt C C O R'
H
R
RCHO (EtO)2P
R NH2
P(OEt)2 O
O
References
[1] For example: Kaboudin, B., Esfandiari, H., Moradi, A., Kazemi, F., Aoyama, H., ZnCl2-Mediated Double Addition of Dialkylphosphite to Nitriles for the Synthesis of 1-Aminobisphosphonates J. Org. Chem. 2019, 84, 14943- 14948.
Curriculum Vitae :
Babak Kaboudin was born in 1970 in Iran. He studied chemistry in Isfahan University (Iran), where he got his bachelor’s degree in chemistry (1992). In the same year, he went to Shiraz University (Iran) and earned his master’s degree in 1994. Then he joined Professor Hashem Sharghi group in Shiraz Institute for Organic Synthesis, where he completed his PhD thesis in September 1998. Subsequently he started his independent research at IASBS (Iran) where he was promoted to full professor in 2007. His research interests include synthesis of biologically active organophosphorus compounds, electrosynthesis, heterocycle synthesis, and the catalytic application of nanomaterials. On academic record, Babak Kaboudin has authored >150 publications in international journals.
6
Total synthesis, a keystone for the discovery of bioactive molecules. Example of polyunsaturated fatty acid metabolites.
Camille Oger
11. Institut des Biomolécules Max Mousseron, UMR 5247, UM, CNRS, ENSCM, FRANCE. Pôle Chimie Balard Recherche, 1919 route de Mende, 34293 Montpellier cedex 5. E-mail: [email protected]
Abstract – Total synthesis remains a major asset for the discovery of new bioactive compounds and biomarkers. Oxidative stress (OS) is a phenomenon that can be found in many pathologies, as a cause and / or consequence of the latter. Polyunsaturated fatty acids (PUFAs) are strongly impacted by this phenomenon and are metabolized in vivo. The metabolites can then be used as biomarkers of OS, and they have intrinsic pharmacological properties.[1]
Кеуwords – Total Synthesis, PUFA, Metabolites, Biomarkers, Bioactive compounds
References
[1] J.-M. Galano, Y. Y. Lee, C. Oger, C. Vigor, J. Vercauteren, T. Durand, M. Giera, J. C.-Y. Lee, Prog. Lipid Res. 2017, 68, 83–108.
Curriculum Vitae : Camille Oger received her PhD in the field of total synthesis of neuroprostanes at the University of Montpellier II, in 2010. She did a post-doctoral work with Pr. Ilan Marek at the Technion- Israel Institute of Technology, working on a new access to stereopentade of polypropionate units. She was promoted assistant professor at the University of Montpellier I in 2011 and obtained her habilitation in 2016 based on her research work on the development of new strategies toward the synthesis of bioactive lipids. In 2017, she received Jean Normant award from the Organic Division of the French Chemical Society.
Her research field is at the interface with chemistry and biology, with the total synthesis of lipids metabolites, the quantification of such compounds in biological fluids and the research of potent biological properties. She is the co-authored of 117 articles and reviews, 4 patents and 2 book chapters. More info on https://camilleoger-chemblog.jimdo.com/
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Design, Synthesis and Application of a new family of compounds Isophosphinoline 2- oxides
Mina Hariri
1,2, Fatemeh Darvish
2, Tahar Ayad
1Patricia Licznar-Fajardo
3, Jean-Luc Pirat
1, David Virieux
11 K.N. Toosi University of Technology, Faculty of Science, Department of Chemistry, Tehran IRAN 2 Institut Charles Gerhardt/UMR 5253/AM2N, Ecole Nationale Supérieur de Chimie de Montpellier, FRANCE
3 Hydro Sciences Montpellier, Univ Montpellier, CNRS, IRD, CHU Montpellier, Montpellier, France E-mail: [email protected]
Abstract – synthesis of a new family of compounds: isophosphinoline 2-oxides, a six-membered phosphorus heterocycle for the discovery of new pharmacophores or bioisosteric groups, to modulate the metabolic and / or pharmacokinetic properties of drugs.
Keyword - Six-membered phosphorus hetrocycle, phenyl phosphonic acid, alkynyl magnesieum bromide, Iso- phosphinoline-2-oxides, 6-endo-dig cycloisomerization.
Reference
[1] M. Hariri, F. Darvish, K.-P. Mengue Me Ndong, N. Sechet, G. Chacktas, H. Boosaliki, M. L. Tran Do, G. Mwande- Maguene, J. Lebibi, A. R. Burilov, T. Ayad, D. Virieux, J.-L. Pirat J. Org. Chem. 2021, 86, 7813−7824.
[2] M. Hariri, F. Darvish, K.-P. Mengue Me Ndong, R. Babouri, J. Lebibi, A. R. Burilov, G. Mwande-Maguene, A. R.
Burilov, P. Licznar-Fajardo, J.-L. Pirat, T. Ayad, D. Virieux, GSC Biological and pharmaceutical science. 2021, 16, 283−296.
Curriculum Vitae :
Mina Hariri received her PhD degree (2021) from the University of K. N. Toosi University of Technology, Tehran, Iran (KNTU) and shed did one year Doctoral internship in ICGM, AM2N group, Institut Charles Gerhardt de Montpellier (ICGM), France. During her PhD research, she was working on Synthesis of pseudo-Chromenes and Terpenoids with Phosphorus-based Allenes and Synthesis and Reactivity of Isophosphinoline 2- oxide.
8
Design a New Silver Protofilament Frameworks (SPFs) as Heterogeneous Catalyst for Coupling Reactions
Vahid Khakyzadeh
ψψ. Department of Chemistry, K. N. Toosi University of Technology, IRAN, Tehran. E-mail: [email protected] Abstract – Metal-organic frameworks (MOFs) have attracted a high interest for their potential usage in many applications such as; energy technologies, catalysis, separation, and so on There are many innovations in this topics, for instance, the first examples of the assembly of a metal–peptide framework (MPFs) was reported by Taubert in 2008 [1]. They constructed MPFs from the interaction of an oligo-valine peptide family with copper to grow porous MPFs.
Their results showed that this MPf is stable up to 250 °C and has some internal porosity and also they mentioned this is the first Bio-inspired Metal-Organic framework (MOFs). Similar to their strategy, we designed a new silver protofilament frameworks as heterogeneous catalyst for coupling reactions. In a nutshell, we found an interesting insect that produced some fibers. Initially, we worked on the identification of the insect, in an international collaboration, then we designed a new catalyst using her natural product.
Кеуwords– Metal Protofilament Framework, Heterogeneous Catalyst, Coupling Reaction.
References
[1] Alexandre Mantion, Lars Massüger, Pierre Rabu, Cornelia Palivan, Lynne B. McCusker, and Andreas Taubert, J.
Am. Chem. Soc. 2008, 130, 8, 2517–2526.
[2] (a) Kun Xu, Vahid Khakyzadeh, Timm Bury, Bernard Breit, J. Am. Chem. Soc. 2014, 136, 16124-16127; (b) Kun Xu, YH Wang, Vahid Khakyzadeh, Bernard Breit, Chemical Science, 2016, 7 (5), 3313-3316; (c) Vahid Khakyzadeh, YH Wang, Bernard Breit, Chem. Commun., 2017, 53 (36), 4966-4968
Curriculum Vitae:
Vahid Khakyzadeh was born in Hamedan, Iran. He received his M.S. and Ph.D.
under the supervision of Professor M.A. Zolfigol from Bu-Ali Sina University, Iran.
During his Ph.D. program, He had this chance to have a 9 months research period in Professor Dr. Bernhard Breit's group as an exchange student. After his Ph.D., He moved to Germany and worked as a post-doctoral researcher in Professor Breit's group for almost 2 years. His topic was Asymmetric Rhodium Catalysis [2].
Subsequently, he started his independent research at K. N. Toosi University of Technology (Iran) in 2016. Presently, His research interests include designing new catalytic systems for C-H bond activation and coupling reactions, and electro organic synthesis. On academic record, Vahid Khakyzadeh has authored >60 publications in international journals and 2 book chapters.
9
Lanthanide-mediated C-F bond activation : tuning the regioselectivity in the reaction of
-difluorinated metal-pentadienyl complexes with aldehydes
10
An Overview of Isocyanide Insertion Reactions, Focusing on Isocyanide Insertion- Cyclization Reactions
Fereshteh Ahmadi
11.Department of Organic Chemistry, K. N. Toosi University, IRAN, Tehran, kavian street, 1541849611, E-mail: [email protected]
Abstract – The isocyanide insertion refers to the direct insertion of isocyanide into a heteroatom- hydrogen, carbon–
hydrogen or carbon–halogen bond to give an imidoylative intermediate, which can be trapped by various nucleophiles.
Nowadays, isocyanide insertion-cyclization reaction (IICR) is one of the most powerful and practical synthetic method in organic synthesis. It directly forms carbon–carbon and carbon-heteroatom bonds in a one step and provides various kinds of heterocycles.
Кеуwords– Isocyanide Insertion, Cyclization, Heterocycles.
References
[1] Ahmadi, F., Goli, H. R., Balmohammadi, Y., Bazgir, A. Isocyanide Insertion–Cyclization Reaction for Imidazoisoindol-5-imine Scaffold Synthesis: A Selective Solvatochromic Fluorescent Probe for Methanol Detection. J. Org. Chem. 2021, 86, 146.
Curriculum Vitae :
Fereshteh Ahmadi was born in 1987 in Qazvin, Iran. She received her B. Sc. Degree from the Imam Khomeini International University of Qazvin in 2010 and her M. Sc.
and Ph. D. degrees from Shahid Beheshti University, Tehran, Iran, in 2012 and 2017.
Her Ph. D. thesis was focused on "Isocyanide Insertion-Cyclization Reactions" under the supervision of Prof. Ayoob Bazgir. In 2016, as Ph.D. visiting student, she joined the group of Prof. Jose Aleman Lara in the Department of Chemistry, University of Autonoma de Madrid (Madrid, Spain) and worked on "Thiol–ene/Oxidation Tandem Reaction Under Visible Light Photocatalysis". She started Postdoctoral Fellow with Prof. Ayoob Bazgir in 2018 at Shahid Beheshti University. During this time, her research was focused on "Synthesis of Florescent Probe for MeOH Detection via Isocyanide Insertion- Cyclization Reactions". In 2019, She joined as an assistant professor at K. N. Toosi University, Iran, where she is still working. Her research interests focus on Isocyanide Insertion Reactions, Organic Synthesis, Organocatalysis and study of the Flurosent Compounds.
11
Multi-Lactamization Reaction for the Conception of Foldamers and Cell Penetrating Vectors
Lubomir L. Vezenkov
1, Alexandre Messerschmitt
1, Baptiste Legrand
1, Vincent Martin
1, Nadir Betache
1, Jean Martinez
1, Muriel Amblard
11 Institut des Biomolécules Max Mousseron (IBMM), UMR 5247 CNRS-Université Montpellier-ENSCM, Pôle Ballard, 226-234 Av. du Professeur Emile Jeanbrau
E-mail: [email protected], ibmmpeptide.com, @teampeptide
Abstract – We developed a simple and versatile multi-lactamization reaction on solid support that allowed us to convert non-structured peptides into highly organized γ-lactam-containing oligomers. We previously showed that poly-(α-amino γ-lactam-α-amino acid) foldamers (poly-Agl-αAA) adopt a bifacial ribbon-like secondary structure with amino acid side chains projected on both sides of the ribbon at a distance of around 9Â (Figure 1A).1
Кеуwords – P
.
References
(1) Martin, V.; Legrand, B.; Vezenkov, L. L.; Berthet, M.; Subra, G.; Calmès, M.; Bantignies, J.-L.; Martinez, J.; Amblard, M. Turning Peptide Sequences into Ribbon Foldamers by a Straightforward Multicyclization Reaction. Angew. Chem. Int. Ed. 2015, 54 (47), 13966–13970.
(2) Vezenkov, L. L.; Martin, V.; Bettache, N.; Simon, M.; Messerschmitt, A.; Legrand, B.; Bantignies, J.-L.; Subra, G.; Maynadier, M.;
Amblard, M. Ribbon-like Foldamers for Cellular Uptake and Drug Delivery. ChemBioChem 2017.
Curriculum Vitae : Lubomir Vezenkov performed a co-tutoring PhD between the universities of Montpellier and Naples, under the supervision of Prof. Jean Martinez and Prof. Ettore Benedetti, which he graduated from in 2011. Afterwards he did a two-years-long post- doctoral internship in the prof. Robert Young group in Simon Fraser University, Vancouver, working on the development of selective inhibitors of the autophagy. In 2013 he moved back to Montpellier and in 2016 he received an associate professor position at The National Graduate School of Chemistry of Montpellier (ENSCM).Lubomir current research focus is in the fields of medicinal chemistry and chemical biology. More precisely he is interested in developing tools for the study of tubulin posttranslational modifications with possible applications for the treatment of neurodegenerative diseases. He is also working in the fields of cell penetrating vectors, foldamers and self-assembling materials.
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Chiral diphenylphosphine dioxides bearing a bis(triazolyl) backbone as promising Lewis bases for asymmetric organocatalysis
Tahar AYAD1
1 Institut Charles Gerhardt/UMR 5253, ENSCM, Pôle Chimie Ballard, 226-234 Av. du Professeur Emile Jeanbrau 34090 Montpellier, FRANCE
E-mail: [email protected]
Abstract – Asymmetric catalysis provides one of the most cost-effective and environmentally responsible methods for the production of a vast array of structurally diverse, enantiomerically enriched molecules, especially for high-value pharmaceutical applications. The obvious benefit of catalytic asymmetric synthesis is that a relatively small amount of enantiopure catalyst containing the chiral information can, in an ideal scenario, produce large quantities of naturally and non-naturally occurring enantiopure products from precursors that may be chiral or achiral. In this regard, chiral phosphine ligands have played a key role in the emergence of asymmetric catalysis. However, fine tuning of the catalytic activity by modification of the stereoelectronic properties of the ligand systems is far from trivial mainly because of the difficulty and cumbersome procedures for structural modification of the ligand scaffolds.1 Over the past few years, our group has been involved in the design and synthesis of new chiral C2-symmetric diphenylphosphine dioxides bearing an original bis(triazolyl) backbone for their use as Lewis bases in asymmetric catalysis.2 Some applications of these new ligands in relevant synthetic transformations will be presented and discussed.3
1 Virieux, D.; Sevrain, N.; Ayad, T.; Pirat, J.-L. Advances in Heterocyclic Chemistry 2015, 116, 37 doi.org/10.1016/bs.aihch.2015.06.001
2 Laborde, L.; Wei, M.-M.; V. D. L, Arie .; Deydier, E.; Daran, J.-C.; Volle, J-N.; Poli, P.; Pirat, J-L.; Manoury, E.; Virieux, D. Dalton Trans., 2015, 44, 12539 doi.org/10.1039/C5DT02197A.
3 a) Sevrain, N.; Volle, J-N.; Pirat, J-L.; Ayad, T.; Virieux, D. RSC Advances, 2017, 7, 52101 doi.org/10.1039/C7RA10919A;
b) Sevrain, N.; Volle, J-N.; Pirat, J-L.; Ayad, T.; Virieux, D. Eur. J. Org. Chem, 2018, 2267 doi.org/10.1002/ejoc.201800317; c) Ayad, T.; Gernet, A.; Volle, J-N.; Pirat, J-L.; Virieux, D. Tetrahedron, 2019, 75, 4385 doi.org/10.1016/j.tet.2019.06.042; d) Gernet, A.; Ratovelomamana-Vidal, V.; Pirat, J-L.; Virieux, D.; Ayad, T. Eur.
J. Org. Chem, 2020, accepted article doi.org/10.1002/ejoc.202001172.
Curriculum Vitae :
Tahar Ayad received his PhD degree (2003) from the University of Toulouse under the supervision of Dr. Y. Genisson and Dr. M. Baltas working on total synthesis of imino sugars that exhibit antituberculosis activity. After his PhD, he was engaged in a post-doctoral position with Professor Robert S. Coleman at The Ohio State University working on total synthesis of Oximidin I and II. After a brief period spent in Toulouse University working as an associate professor in R. Chauvin's group in 2005, he joined the group led by Professor J.-P. Genet and Dr. V. Vidal at the Ecole Nationale Superieure de Paris, Chimie ParisTech. His present research fields at the Ecole Nationale Superieure de Montpellier include ligands synthesis, transition metal-catalyzed asymmetric reactions and, the synthesis of biologically relevant active compounds.
13
From strained phosphine oxide to original atropochiral ligand: an ImperialPhos story Lucas Mele
1, Rachida Babouri
1, Jean-Luc Pirat
1, Tahar Ayad
1And David Virieux
1.
1 Chimie et Matériaux Moléculaires, Institut Charles Gerhardt Montpellier, Montpellier, France E-mail: [email protected]
Abstract – Conformationally restrained bridgehead phosphine oxide derivatives, such as 1-phosphabicyclo[3,3,1]- nonanes 1 (also called methanophosphocines) were originally described by Issleib in the late seventies. They were obtained through the radical cyclization of unsaturated and pyrophoric primary alkenylphosphines.1 We
reinvestigated such approach using a double gold-catalyzed cyclization of bis(arylmethyl)ethynylphosphine oxides 2 to afford a collection of methanophosphocines.2 The last decade has seen the emergence of strained cyclic phosphine oxides which showed diverse applications in organocatalysis. The best catalysts showed a clear tendency to narrow the heterocyclic core thus facilitating the key reduction step.3 In this context, conformationally restrained bridgehead phosphine oxides are yet to be explored. Next, we engaged dibromo derivative 1 with a variety of arylboronic acids in Suzuki-Miyaura coupling. After optimization, the reaction proceeded smoothly and afforded the expected bis(biaryl) methanophosphocines 3 in moderate to high yields. Ortho-substituted unsymmetrical derivatives presented an original combination of axial and central chirality. Such unusual symmetry and the corresponding chirality will be discussed.
Keywords – Strained phosphine oxides, atropochirality, gold cyclisation, phosphorus.
References
[1] F. Krech, K. Z. Issleib, Z. Anorg. Allg. Chem., 1976, 425, 209−216.
[2] R. Babouri, L. Traore, Y.-A. Bekro, V. I. Matveeva, Y. M. Sadykova, J. K. Voronina, A. R. Burilov, T. Ayad, J.-N. Volle, D. Virieux, J.-L. Pirat, Org. Lett., 2019, 21, 45–49.
[3] L. Longwitz, A. Spannenberg, T. Werner, ACS Catal., 2019, 9, 9237–9244.
Curriculum Vitae :
Lucas Mele was graduated from the Ecole Normale Supérieure Paris-Saclay in 2020. He obtained a master’s degree in organic Chemistry from Université Paris- Saclay and an engineering degree from Chimie Paristech. Currently, he is in PhD under the guidance of Prof. D. Virieux. His research work is focused on the development of phosphorus-based small molecules for therapies in neurodegenerative diseases.
