Asymmetric Remote Functionalisation Through Metallotropy – METALATE

Synthetic approaches for the construction of added-value organic molecules are in continuous progress. Until recently, the surge in cutting-edge synthetic approaches such as those based on C-H and C-C bond activations has produced a deep change in the way the chemist designs synthetic routes. And yet, in spite of key achievements made, all these approaches usually keep as common denominator the fact that a reagent/catalyst interacts with the most reactive site of a substrate (= initiation site) where a selective transformation then occurs. The initiation and functionalisation sites therefore coincide. Dissociating the initiation site from the functionalisation site is often challenging but may prove to be a powerful synthetic strategy. As the two sites are structurally distant, a communicative process between them through external or internal induction is needed. The one through external induction can lead to amazing results but usually requires a high-molecular weight template that has to be removed once the transformation is achieved. The one through internal induction implies the internal migration of the reagent/catalyst along the substrate backbone. In this context, while the metal promenade triggered by C–C double bond migration is a well-explored area, the same process through metallotropy remains a black box. The METALATE project aims at developing asymmetric remote functionalisations through metallotropry triggered by dearomatisation/ rearomatisation and involving zincate reagents.