Thiamine-inspired novel organocatalytic reactions with heterazolium precatalysts

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With respect to the continuously increasing complexity of organic target molecules the ongoing development of new synthetic methods and improvement of known transformations can be seen as a perpetual goal of chemical research. In this context, organocatalytic processes are gaining importance in the field of asymmetric synthesis; in particular as these methods otter both easy to- handle, metal-free reaction conditions and, moreover, new modes of actions for catalytic transformations, such as umpolung reactivity. Within the scope of this project the improvement of N-heterocyclic carbene (NHC)-catalyzed reactions will be attempted in a synergistic, multidisciplinary approach. At the interface of enzyme and organic catalysis we aim to transfer insights from both fields in a bidirectional way to allow for improvement and development of new methods. With this prerequisite it is the objective of this project to mimic the activity of thiamine diphosphate (ThDP)-dependent enzymes. Specifically, we will investigate catalytic bondcleaving reactions for the synthesis of w-functionalized molecules based on their enzymatic archetypes and additionally, apply insights into the Stereodifferentiation within the enzymes active sites to improve stereoinduction in carbene catalysis. A further goal of this project is the application of synthetic based knowledge to enzyme catalysis, which will be realized in cooperative projects including the employment of alternative substrates and the implementation of novel coenzyme analogues for ThDP-dependent enzymes.