Although the halogenation of organic molecules is one of the most widespread techniques for the functionalization of substrates, efficient catalytic methods for the selective (regio-, chemo-, and in particular stereoselective) construction of carbon-halogen bonds are rare. In contrast, Nature has evolved different strategies to create carbon-halogen bonds in a highly effective and specific manner.

Our research therefore focuses on the exploration of the mechanism as well as the structure-function relationship of such halogenation catalyzing enzymes. Based on these findings mild, generally applicable, and selective catalytic methods for the formation of carbon-halogen bonds (brominations, chlorinations and even fluorinations) are developed combined with their application to access medically relevant target structures in efficient ways. Selected examples of our group imitating Nature’s concepts of halogenation reactions will be presented, in particular those utilizing hypervalent λ³-iodanes¹and Lewis base-Lewis acid cooperative networks.²These strategies help to push the boundaries of chemical space as they grant access to a rich diversity of novel chemical structures that often cannot be approached by our current standard method repertoire.

[1] a) A. M. Arnold, A. Ulmer, T. Gulder, T., Chem. Eur. J. 2016, 22, 8728; b) S. V. Kohlhepp, T. Gulder,  Chem. Soc. Rev. 2016, 45, 6270; c) Andries-Ulmer, A.; Brunner, C.; Rehbein, J.; Gulder, T. J. Am. Chem. Soc. 2018, 140, 13034.
[2]  A. M. Arnold, A. P., M. Drees, T. Gulder J. Am. Chem. Soc. 2018, 140, 4344.