Asymmetric Catalysis Promoted by Sigma-Hole Interactions

Asymmetric catalysis is the most useful way to provide enantioenriched compounds for various
applications, especially therapeutic ones. Such catalysis mostly relied on metal-based catalysts. Due
to toxicity problem associated with their use, organocatalysts have emerged as an alternative.
Although improvement has been achieved, organocatalysts mostly rely on hydrogen bond and usually
cannot achieve yields and enantioselectivities as high as their metallic counterparts. It is therefore
judicious to open and evaluate new paradigms in organocatalysis.
Developing new and efficient halogen- or chalcogen bond based organocatalysts is such a
breakthrough, and this is the aim of the AsymHole project. New chiral structures based on 4,4’-
bipyridine and ferrocene units bearing iodine or chalcogen as well as on disubstituted iodo or
chalcogeno units are envisaged in this project. With the aid of calculations and of physicochemical
studies, the catalysts properties will be evaluated in solution and in the solid state in order to get
information on their enantiorecognition ability and to identify the atoms and functions that really
participate in sigma-hole based interactions. The so-obtained compounds will then be applied as
catalysts into selected organic reactions, classical ones for benchmarking and more challenging ones.
Feedback loops will be set up between results and calculations in order to optimize these