Periodic Reporting for period 4 - UNBICAT (Unconventional Bifunctional Catalysts) Reporting period: 2020-03-01 to 2021-08-31 Summary of the context and overall objectives of the project Over recent years in this project we have managed to consolidate two areas in the research group concerning the use of sustainable processes, in the field of photocatalysis and organocatalysis. Thus, we have described new activation processes for silylated compounds, which constitutes an alternative to the traditional methods, and also with very good enantiomeric excesses. While in the second part of the project, we have used new bifunctional organocaphotocatalysts for different reactions, such as aldehyde alkylations, cycloaddition reactions, among many others. Therefore, thanks to this project we have developed an arsenal of different methodologies, which will allow our group and other research groups new possibilities within asymmetric catalysis. Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far The UNBICAT project has obtained very good results both in quantity and quality of the publications obtained, giving rise to relevant results, published in prestigious journals such as Nature Communs, Angewandte Chem., J. Am. Chem. Soc, Chemical Sciences, among others (for the completed list, see www.uam.es/jose.aleman). In addition, the results throughout these years have been disseminated in different prestigious national and international forums. Some additional activities of our groupa) On the radio and news about our group: https://goo.gl/NMstWD. About our research in materials: https://goo.gl/Xw21zG; On Onda-Cero; https://www.youtube.com/watch?v=8LpEsYt4SaQ; materials: https://goo.gl/T8Ysuo In La Vanguardia newspaper: https://bitly.com/; b) Meet the fellows in Spain: see: https://goo.gl/GT7MyE; We performed photochemical experiments to general audience. c) In UAM-green technologies https://www.youtube.com/watch?v=yrwxLwjGueg d) Personal interview to Dr. Alemán: https://www.youtube.com/watch?v=zf9uhxDpUg8 c) About Catalysis: Chemical Journals: https://goo.gl/EJSaM4 https://goo.gl/xJjVxp; and in the following chemistry portal: https://goo.gl/S1s2rQ d) Our manuscripts have been highlighted in different cover pictures (CEJ 2018, 24, 3117, CEJ, 2016, 46, 16467), as VIP ARTICLE (CEJ, 2016, 46, 16467); Cover-picture in ACS Appl. Mater. Interfaces 2021, 13, 21, 24877, or in Synfacts (last years): Synfacts 2014, 10, 978 Synfacts 2017, 10, 978 Synfacts, 2018, 984. Synfacts 2018, 14, 1133. Synfacts 2020, 16, 0478. Synfacts, 2021. 17, 385.f) Organization of the second workshop of catalytic materials, UAM, 20/04/2018 (120 researchers) and the 4th Photoart workshop of materials (70 researchers, 16/10/2021).g) Some of our manuscripts highlighted in UAM-media and blogs, see e.g: https://bit.ly/3CvSd3B ; https://bit.ly/2Zjkj3S ; https://bit.ly/3EwNrEZ ;https://bit.ly/39n9UFU ;h) We have a quite active twitter account for the group: @jaleman2, in which is announce new publications, positions, and also research horizons of the group.i) In 2020 and 2021 European Researchers’ Night, members of the group have organized a new activity called “the lab of superheroes Marvel”. https://bit.ly/39wcCJe j) Talking about Organocatalysis and Nobel Prized 2021 in RNE: https://shorturl.at/cjkKU ; https://shorturl.at/ivILM Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far) In the last years, our research group has been developing new organocatalytic processes in two main areas and covalent catalysis. For example, we have contributed to the activation of silyldienol ethers, obtaining interesting Bayllis-Hillman and Rauhut-Currier type products, as well as remarkable nitrogen additions applied to the synthesis of aminoacids or the development of inverse-electron demand aza-Diels-Alder reactions. In the field of photocatalysis, we have contributed with the development of new photocatalysts, such as acridinium-type salts, bifunctional aminocatalysts, platinum-bearing systems, or diamine-derivatives for [2+2] cycloadditions. In addition, we have studied and described new photocatalytic processes, such as ring expansion reactions, tandem processes, alkylations, or heterocyclic syntheses. During these investigations, the degradation of the photocatalyst, and in occasions the required high catalytic loadings, prompted us to explore new horizons in our research, such as the use of materials. Thus, in the catalytic material field, we have focused on the application of our knowledge in photocatalysis and organocatalysis for its implementation in heterogeneous systems. Thus, we have incorporated platinum photocatalytic centers in mesoporous silica materials (J. Catal. 2019, 374), or Covalent Organic Frameworks (COF) using a novel strategy (Applied Catal. B, 2020, 119027). Our interest was also related to the use of COF with heterobimetallic structures (ACS-Catal, 2021, 11, 12344), or the incorporation of organic photocatalysts to mesoporous materials (J. of Materials Science, 2022, 103, 134) and carbon nanotubes (ACS Appl. Mater. Interfaces 2021, 24877). These initial explorations on catalytic materials, has given us a practical idea of the advantages and limitations of each class of materials (COF, nanotubes, and mesoporous silica).