Synthetic tools for the rapid construction of (stereoisomerically) pure building blocks and intermediates for target-oriented synthesis are cornerstones in the foundation of the science of synthesis. The prerequisite for improving catalytic systems and to design new catalysts is the understanding of controlling the reaction kinetics. Therefore the development of techniques to comprehensively investigate the reaction kinetics of a variety of substrates is of great interest. In particular the investigation of individual pathways in stereoselective reactions requires techniques to directly access enantioselectivities. Nonlinear effects arising from molecular association of enantiomers in nonracemic mixtures can cause unexpected effects, i.e. in chiroptics, NMR spectroscopy only to mention a few. Furthermore determining kinetic data of stereoselective catalyzed rearrangements can be complicated at elevated temperatures by overlaying non-stereoselective thermal conversions and even more so when observing competing reactions or isomerization of stereoisomeric reactants. Here, we will demonstrate that integration of (stereoselective) catalysis and (stereoselective) chromatography is possible and constitutes a valuable tool to rapidly access reaction kinetics and selectivities with high precision, because using only minute amounts of reactants allows determining the reaction rate constant at a given temperature and under constant reaction conditions. Examples including the asymmetric Gosteli-Claisen rearrangement, the development of a modular screening platform for NHC ligands, enantioselective hydrogenations and other reactions will be presented. Furthermore, the detailed investigation of a chemical process starting from renewable feedstock to valuable compounds using on-column reaction gas-chromatography and the transfer of these results to lab-scale reactors and the pilot-plant will be shown. References Stockinger, S.; Gmeiner, J.; Zawatzky, K.; Troendlin, J.; Trapp, O. Chem. Commun. 2014, 50, in press. Gmeiner, J.; Seibicke, M.; Lang, C.; Gärtner, U.; Trapp, O. Adv. Synth. Catal. 2014, 356, 2081-2087. Maier, F.; Trapp, O. Angew. Chem. Int. Ed. 2012, 51, 2985-2988. Troendlin, J.; Rehbein, J.; Hiersemann, M.; Trapp, O. J. Am. Chem. Soc. 2011, 133, 16444-16450.

From screening of (enantioselective) catalysts by integration of analysis and synthesis to the application in a pilot plant

249th National Meeting (2015)

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