On July 27, 2023, CRC1333 project leader Sabine Laschat from projects A08 and B03 gave a talk at this year’s OMCOS XXI conference in Vancouver, Canada. The topic of her talk was “Asymmetric Rh Diene Catalysis under Liquid and Solid Confinement – When Polarity, Domain Size and Flexibility Matter”.
OMCOS XXI, which took place from July 24 until July 28 this year, is a single session scientific conference that brings together industrial and academic chemists from around the world to discuss recent advances in metal-mediated and -catalyzed reactions. The conference focused on catalyst/ligand design, mechanistic insights, new processes/automation, novel preparations and uses for organometallic reagents, as well as the synthesis of pharmaceuticals, fine chemicals, agrochemicals and materials. More information can be found here.
“Asymmetric Rh Diene Catalysis under Liquid and Solid Confinement – When Polarity, Domain Size and Flexibility Matter” – Talk Abstract:
Asymmetric catalysis with chiral Rh diene complexes has received increasing interest over the last two decades.1 Taking inspiration by enzymes, researchers have recognized the important role of confinement on catalytic reactions with respect to reaction rate, yield, mechanism, product ratio, chemo- and regioselectivity, diastereomeric and enantiomeric ratio.2-4 However, confinement effects have only been rarely exploited in Rh diene catalysis. Therefore, we studied the Rh-catalyzed 1,2-addition of phenylboroxine to N-tosylimines as a benchmark reaction both under liquid confinement in microemulsions5,6 as well as solid confinement in mesoporous silica SBA-157 and silica-inverse opals SiO2-IO.8 The role of polarity (and charge), domain or pore size, steric bulkiness and flexibility of linkers between catalyst and support in such confined catalyses will be discussed and methods to determine the accessibility and spatial distribution of Rh diene complexes in pores will be presented.
References
[1] Huang, Y.; Hayashi, T. Chem. Rev. 2022, 122, 14346-14404.
[2] Poli, R. (ed.), Effects of Nanoconfinement on Catalysis, Springer International Publishing, Cham, 2017.
[3] Lyu, Y.; Scrimin, P. ACS Catal. 2021, 11, 11501-11509.
[4] Wang, K.; Jordan, J. H.; Hu, X.-Y.; Wang, L. Angew. Chem. Int. Ed. 2020, 59, 13721-13721.
[5] Deimling, M.; Kirchhof, M.; Schwager, B.; Qawasmi, Y.; Savin, A.; Mühlhäuser, T.; Frey, W.; Claasen, B.; Baro, A.; Sottmann, T.; Laschat, S. Chem. Eur. J. 2019,25, 9464-9476.
[6] Kirchhof, M.; Abitaev, K.; Abouhaileh, A.; Gugeler, K.; Frey, W.; Zens, A.; Kästner, J.; Sottmann, T.; Laschat, S. Chem. Eur. J. 2021,27, 16853-16870.
[7] Beurer, A.-K.; Kirchhof, M.; Bruckner, J. R.; Frey, W.; Baro, A.; Dyballa, M.; Giesselmann, F.; Laschat, S.; Traa, Y. ChemCatChem 2021,13, 2407-2419.
[8] Deimling, M.; Kousik, S. R.; Abitaev, K.; Frey, W.; Sottmann, T.; Koyonov, K.; Laschat, S.; Atanasova, P. ChemCatChem 2021,13, 2242-2252.
[9] Rieg, C.; Kirchhof, M.; Gugeler, K.; Beurer, A.-K.; Stein, L.; Dirnberger, K.; Frey, W.; Bruckner, J. R.; Traa, Y.; Kästner, J.; Ludwigs, S.; Laschat, S.; Dyballa, M. Catal. Sci. Technol. 2023, 13, 410-417.