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Development of Novel Continuous Flow Methodologies Using Metal Catalysts: Applications in Drug Synthesis

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Development of Novel Continuous Flow Methodologies Using Metal Catalysts: Applications in Drug Synthesis Universidad CEU San Pablo CEINDO – CEU Escuela Internacional de Doctorado PROGRAMA en CIENCIA Y TECNOLOGÍA DE LA SALUD Development of novel continuous flow methodologies using metal catalysts: Applications in drug synthesis TESIS DOCTORAL Presentada por: Jorge García Lacuna Dirigida por: Javier Pérez Castells y Gema Domínguez Martín MADRID 2020 A mis padres #Nuncadejesdecreer This PhD has been supervised by Prof. Javier Pérez Castells and Prof. Gema Domínguez Martín. I would like to thank both their patience, closeness, and support. I want to acknowledge to Prof. Javier Pérez Castells that he always relied on me and gave me the opportunity to work in his group since I met him when I was a 3rd year Pharmacy student. I acknowledge Prof. Gema Domínguez for the way she teaches and works, so powerful, energetic, and cheerful that made the daily work easier and enjoyable. I have to admit that I was incredibly lucky to have Dr. Jaime Blanco-Urgoiti as industrial partner. He acted as another mentor and that is something very enriching and rewarding. I would like to acknowledge him for all his teachings and guidance. I wish to thank Prof. C. Oliver Kappe for giving me the opportunity to work in his group for 4 months, and Prof. C. A. Hone for his advices, help and support. I really appreciated my stay in Graz. Alberto, Álex y Jose María were my lab mates during these 4 years. I would like to thank them the great experience that has been working together. The atmosphere in the laboratory has been incredible and pleasant. They have become good friends and I hope this will remain for a long time. Moreover, I would like to thank to all the Master and undergraduate students that have passed around the lab. Especially, all the ones that have worked with me and did their bit in the work that I have done these years: Lucia M., Gilbert S., Raquel R., Elena V., Naiara P., Miryam G., Mateo C. and Javier M. In the same way, I thank the Medicinal Chemistry group for his advices and resources. I cannot conclude this report without expressing my gratitude to my family, especially my parents for their unflagging support and comprehension since the very first day of this Ph.D. Thanks also to all my friends with whom I have shared good and bad times over these years. This thesis, titled: ‘Development of novel continuous flow methodologies using metal catalysts: Applications in drug synthesis’, is presented as a collection of publications with the agreement of my supervisors: Prof. Javier Pérez Castells and Prof. Gema Domínguez Martín. We have followed the requirements approved by the Direction committee of CEINDO on the 30th of November of 2017. In the aim to achieve the International PhD supplement we have followed the corresponding indications and thus this report is written in English and includes a brief summary in Spanish. This Ph.D. was carried out in the Chemistry and Biochemistry department, of the Pharmacy faculty, San Pablo CEU University (Madrid, Spain). This thesis has given rise to the following publications: • J. García-Lacuna, G. Domínguez, J. Pérez-Castells, ChemSusChem 2020, 13, 5138- 5163. DOI: 10.1002/cssc.202001372 • J. García-Lacuna, G. Domínguez, J. Blanco-Urgoiti, J. Pérez-Castells Org. Biomol. Chem. 2019, 17, 9489-9501. DOI: 10.1039/C9OB02124H • J. García-Lacuna, G. Domínguez, J. Blanco-Urgoiti, J. Pérez-Castells Org. Lett. 2018, 20, 5219-5223. DOI: 10.1021/acs.orglett.8b02168 • J. García-Lacuna, G. Domínguez, J. Blanco-Urgoiti, J. Pérez-Castells Chem. Commun. 2017, 53, 4014-4017. DOI: 10.1039/C7CC01749A. In addition, the following publication includes part of my work during my internship in the group of Prof. C. O. Kappe (University of Graz, Austria). • M. Prieschl, J. García-Lacuna, R. Munday, K. Leslie, A. O'Kearney-McMullan, C. A. Hone, C. O. Kappe Green Chem. 2020, 22, 5762-5770. DOI: 10.1039/D0GC02225J The bibliometric data on the journals were these articles have been published are presented in the corresponding chapters. Madrid, October 2020 Prof. Gema Domínguez Martín Prof. Javier Pérez Castells Table of contents 1. General introduction ................................................................................ 1 2. Aims and background .............................................................................. 3 2.1. Flow chemistry .............................................................................. 6 2.2. The Pauson–Khand reaction (PKr) ............................................. 15 2.2.1. Historical overview and general considerations ............ 15 2.2.2. Vinyl ethers as substrates for the PKr. ......................... 22 2.2.3. The PKr in flow reactors. .............................................. 22 2.2.4. Pauson Khand applications in total synthesis: Treprostinil .................................................................................. 23 2.3. [2+2+2] Cycloaddition .................................................................. 26 2.3.1. Co catalyzed [2+2+2] cycloaddition .............................. 29 2.4. References .................................................................................. 37 3. La reacción de Pauson-Khand en flujo continuo. ................................... 43 4. Síntesis de Treprostinil utilizando metodología de flujo para las reacciones clave: Pauson-Khand y reordenamiento de Claisen ......................................... 49 5. Ciclotrimerizaciones de alquinos y cicloadiciones [2+2+2] cruzadas en un reactor de flujo .................................................................................................. 65 6. Reacciones de cicloadición en flujo. ...................................................... 73 7. Hidrogenación de un éster en flujo catalizada por rutenio ................... 101 8. Conclusions ......................................................................................... 113 9. Resumen y conclusiones ..................................................................... 115 General introduction 1. General introduction The general aim of this PhD is the development of novel methodologies in continuous flow reactors in order to carry out metal catalyzed reactions. We have focused on homogeneous dicobalt octacarbonyl catalyzed cycloadditions. Applications in the synthesis of one pharmaceutical is also shown. First, a new protocol for a cobalt catalyzed Pauson-Khand cycloaddition in a flow reactor is developed. The Pauson-Khand reaction in flow had only one precedent in the literature. However, our protocol significantly improves the previous methodology as it is is catalytic, scalable and with broader scope. Our methodology was published as a communication, in a multidisciplinary chemistry journal due to its broad interest and high applicability. Thus, we chose Chemical Communicatios, a high impact journal (Impact factor of 6.297 in 2017, Q1) published by the Royal Society of Chemistry. After this general study of reaction conditions and scope was finished, the novel procedure was applied to the total synthesis of the drug Treprostinil, where the key catalytic Pauson-Khand reaction (PKr) was performed in flow. This chapter includes, mainly, organic synthetic work applied to the improvement and scalability of the synthesis of this drug. Therefore, we selected the journal Organic & Biomolecular Chemistry (Impact factor 3.412 in 2019, Q1) for the publication, as it is specialized in new or significantly improved protocols or methodologies in total synthesis of natural products or pharmaceuticals. Furthermore, a new protocol that allows the use of vinyl ethers as substrates for the PKr is being developed, which will lead to a novel synthesis of multisubstituted tricyclic benzofurans. The results of this latter study have not been published yet. In another chapter of this report, a new protocol that uses the same catalyst for alkyne cyclotrimerizations and crossed [2+2+2] cycloadditions using a flow reactor is developed. Organic 1 General introduction letters was the chosen journal for the publication of this work, which is a high impact journal in the field of organic chemistry (6.555 of impact factor in 2018, Q1). Finally, during the thesis period we carried out an extensive literature revision and analysis of all the cycloadditions performed using continuous flow methodologies. We evaluated the benefits gained by each kind of cycloaddition in flow, by comparison with traditional methodologies. The remaining challenges and the future perspectives were addressed. The resulting review manuscript was published in ChemSusChem journal, a high impact journal (Impact factor of 9.762 in 2019, Q1) focused on sustainable chemistry. Furthermore, a publication which includes part of the work done during my research stay in C. O. Kappe´s group is also presented. The work involves a metal catalyzed reaction, using a gas-liquid regime, optimized using a flow reactor. This work was published in Green Chemistry, due to the great sustainable progress of the contribution. This journal is specialized in innovative research on the development of alternative green and sustainable technologies and had an impact factor of 9.480 in 2019 (Q1). The paper is part of a larger project that will also be published in the future. 2 Aims and background 2. Aims and background This report includes contributions that deal with two different fields of organic and organometallic synthesis performed in flow: The Pauson-Khand reaction and [2+2+2] cycloadditions. After presenting the main goals of this thesis we include a background section where we summarize
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