XXI INTERNATIONAL SYMPOSIUM „ADVANCES IN THE CHEMISTRY OF HETEROORGANIC COMPOUNDS” ORGANIZED BY Centre of Molecular and Macromolecular Studies Polish Academy of Sciences Section of Heteroorganic Chemistry Polish Chemical Society in cooperation with Faculty of Mathematics Faculty of Chemistry and Natural Sciences Łódź Branch University of Łódź Jan Dlugosz University Polish Chemical Society in Czestochowa ŁÓDŹ, November 23, 2018 Printed by PIKTOR Szlaski i Sobczak Spółka Jawna, Tomaszowska 27, 93-231 Łódź, 2018. ISBN 978-83-7455-585-2 http://www.cbmm.lodz.pl/ XXI International Symposium “Advances in the Chemistry of Heteroorganic Compounds” is dedicated to Professor Tadeusz Gajda and Professor Janusz Zakrzewski on the occasion of their 70th birthday Conference Chairman Józef Drabowicz Organizing Committee Bogdan Bujnicki Tomasz Cierpiał Ignacy Janicki Piotr Kiełbasiński Dorota Krasowska Jerzy Krysiak Piotr Łyżwa Aneta Rzewnicka Wanda H. Midura Sponsored by XXI International Symposium “Advances in the Chemistry of Heteroorganic Compounds” Programme Friday, November 23 9:00 – 9:30 OPENING SESSION I – chairman: Tadeusz Gajda Stefano Menichetti University of Florence, Italy 9:30 – 10:15 PL-1 Synthesis and selected properties of heterohelicenes: A new twist on our chemistry György Keglevich 10:15– 11:00 PL-2 Budapest University of Technology and Economics, Hungary Microwave irradiation and catalysis in organophosphorus chemistry – green synthesis of organophosphorus compounds 11:00 – 11:20 COFFEE BREAK 11:20 – 12:50 POSTER SESSION 12:50 – 13:50 LUNCH SESSION II – chairman: Janusz Zakrzewski Peter Metz 13:50 – 14:35 PL-3 Technische Universität Dresden, Germany Total Synthesis of Diterpene Natural Products Claudio Santi 14:35 – 15:20 PL-4 University of Perugia, Italy Organoselenium Compounds in Catalytic Reactions Masaichi Saito Saitama University, Japan 15:20– 16:05 PL-5 Expansion of Aromaticity: From π-Aromaticity to σ+π-Double Aromaticity Luca Sancineto Centre of Molecular and Macromolecular Studies Polish Academy of Science, Poland 16:05 – 16:35 PL-6 University of Perugia, Italy An Organoselenium Catalyzed Strategy for Oxidation Reactions Compounds 16:35 – 16:50 CLOSING PL - plenary lecture PLENARY LECTURES PL-1 Synthesis and selected properties of heterohelicenes: A new twist on our chemistry Stefano Menichetti and Caterina Viglianisi Department of Chemistry ‘Ugo Schiff’, University of Florence, Via Della Lastruccia 3-13, 50019, Sesto Fiorentino, Firenze, Italy [email protected] Helicenes and heterohelicenes are challenging chiral structures that continuously stimulate new interest and find new applications. From just a chemical curiosity related with their inherent chirality, these compounds are now commonly used in asymmetric synthesis, medicinal chemistry and, above all, material science.1 In the last years we became interested in the chemistry of heterohelicenes and we described new approaches for their synthesis. For example, we demonstrated that with the proper design of the reagents, the Povarov reaction can be exploited for the synthesis of [4], [5] and [6]azahelicenes.2 At the same time we showed that thia-bridged triarylamine[4]helicenes can be prepared using consecutive regioselective electrophilic sulfur insertions on triarylamines or N-arylphenothiazines.3 Due to the length of the four carbon-sulfur bonds, these peculiar systems belong to the valuable family of stereochemically stable [4]helicenes with racemization barriers as high as 31-32 Kcal/mol. In this communication, scope and limitation of the above procedures as well as preliminary investigations of the properties of these heterohelicenes will be discussed. References [1] a) Y. Shen, C-F. Chen Chem. Rev. 2012, 112, 1463–1535; b) M. Gingras Chem. Soc. Rev. 2013, 42, 968-1006. [2] C. Viglianisi, C. Biagioli, M. Lippi, M. Pedicini, C. Villani, R. Franzini, S. Menichetti, Eur. J. Org. Chem. 2018, DOI: 10.1002/ejoc.201801489. [3] a) G. Lamanna, C. Faggi, F. Gasparrini, A. Ciogli, C. Villani, J. P. Stephens, J. F. Devlin,; S. Menichetti, Chem-Eur. J., 2008, 14, 5747-5750. b) S. Menichetti, C. Faggi, M. Onori, S. Piantini, M. Ferreira, S. Rocchi, M. Lupi, I. Marin, M. Maggini, C. Viglianisi, Eur. J. Org. Chem. 2018, DOI: 10.1002/ejoc.201801493. PL-2 Microwave irradiation and catalysis in organophosphorus chemistry – green synthesis of organophosphorus compounds Dedicated to Prof. Marian Mikołajczyk on the occasion of his 80th Birthday György Keglevich Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, H-1521 Budapest, Hungary [email protected] The microwave (MW) technique has become an important tool in organophosphorus chemistry [1–3]. In this paper, the advantages of MWs in different catalytic reactions are surveyed. The first case is, when the MW-assisted direct esterification of phosphinic acids becomes more efficient in the presence of an ionic liquid catalyst (A) [4]. The second instance is, when catalytic reactions, such as the phase transfer catalyzed (PTC) O-alkylation of phosphinic acids (B), or the Arbuzov reaction of aryl bromides (C) are promoted further by MW irradiation. It is also an option that MWs may substitute catalysts, such as in the PTC alkylation of active methylene containing P-derivatives (D) [5], in Kabachnik–Fields condensations (E) [6], and in reluctant P=O deoxygenations (F) [7]. Another valuable finding of ours is that in the Hirao P–C coupling applying Pd(OAc)2 as the catalyst, the slight excess of the >P(O)H reagent may substitute the usual P-ligands (G) [8]. It is also the purpose of this paper to elucidate the scope and limitations of the MW tool [2,3], to interpret the special MW effects, and to model the distribution and effect of the local overheatings [9,10]. All these considerations were possible on the basis of the results of our quantum chemical calculations, and utilizing the pseudo first order kinetic equation and the Arrhenius equation. References [1] G. Keglevich, E. Bálint, N. Z. Kiss, in: Milestones in Microwave Chemistry – SpringerBriefs in Molecular Science, Ed.: G. Keglevich; Springer, Switzerland, 2016, pp. 47-76. [2] G. Keglevich, N. Z. Kiss, A. Grün, E. Bálint, T. Kovács, Synthesis, 2017, 49, 3069. [3] G. Keglevich, Chem. Rec., 2018, in press. [4] N. Z. Kiss, G. Keglevich, Tetrahedron Lett., 2016, 57, 971. [5] G. Keglevich, E. Bálint, A. Grün, Catalysts, 2015, 5, 634. [6] G. Keglevich, E. Bálint, Molecules, 2012, 17, 12821. PL-2 [7] T. Kovács, G. Keglevich, Curr. Org. Chem., 2017, 21, 569. [8] G. Keglevich, R. Henyecz, Z. Mucsi, N. Z. Kiss, Adv. Synth. Catal., 2017, 359, 4322. [9] G. Keglevich, I. Greiner, Z. Mucsi, Current Org. Chem., 2015, 19, 1436. [10] G. Keglevich, N. Z. Kiss, Z. Mucsi, Milestones in microwave-assisted organophosphorus chemistry. Pure Appl. Chem., 2016, 88, 931. PL-3 Total Synthesis of Diterpene Natural Products Peter Metz Faculty of Chemistry and Food Chemistry - Organic Chemistry I, Technische Universität Dresden, Bergstrasse 66, 01069 Dresden (Germany) [email protected] A concise total synthesis of the neoclerodane diterpene salvinorin A, isolated from the leaves of the Mexican medicinal plant Salvia divinorum, was achieved commencing with 3-furaldehyde (Scheme 1). Two highly diastereoselective intramolecular Diels–Alder reactions (IMDA) were used as the key transformations.[1] Scheme 1. The first total synthesis of the diterpene 3-hydroxy-7-kemp-8(9)-en-6-one, isolated from the soldier defense secretion of higher termites, has been accomplished starting from the Wieland-Miescher ketone (Scheme 2). A diastereoselective sulfa-Michael addition enabled the generation of the delicate ,-unsaturated ketone moiety, while the tetracyclic kempane skeleton was readily constructed through domino metathesis.[2] Scheme 2. Acknowledgements This work was supported by the Deutsche Forschungsgemeinschaft (ME 776/20-2, ME 776/17-2). References [1] Y. Wang, P. Metz, Org. Lett., 2018, 20, 3418-3421. [2] Y. Wang, A. Jäger, M. Gruner, T. Lübken, P. Metz, Angew. Chem., 2017, 129, 16076-16081; Angew. Chem. Int. Ed., 2017, 56, 15861-15865.. PL-4 Organoselenium Compounds in Catalytic Reactions Santi Claudio Department of Pharmaceutical Sciences, UNIVERSITY of PERUGIA Italy [email protected] One of the most interesting aspect of organoselenium chemistry is the possibility to perform functional group conversions or selenofunctionalization under catalytic conditions. Electrophilic selenation-deselantion (A), oxygen transfer reactions (B) and iodine catalysed selenofunctionalization (C) will be here discussed focusing the attention on the most recent results using non-conventional conditions and the first examples of selenium catalysed processes under flow conditions.[1] oxidant substrate oxidant A R-SeSe-R R-Se R-Se substrate product R-Se peroxide peroxide substrate B R-SeSe-R R-SeO2H R-SeO3H substrate[O] R-SeO2H oxidant I C 2 substrate R-SeSe-R R-Se-I R-Se substrate I2 Scheme 1. References [1] E. J. Lenardao, C. Santi, L. Sancineto New Frontiers in Organoselenium Compounds, 2018. Springer International Publishing (Springer Nature). PL-5 Expansion of Aromaticity: From π-Aromaticity to σ+π-Double Aromaticity Masaichi Saito Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama-city, Saitama, 338-8570, Japan [email protected] Since the discovery of benzene, aromaticity has been utilized to explain unique properties of benzene and its derivatives. The aromaticity