The catalyzed intermolecular hydroamination of alkenes and more specifically its enantioselective version is nowadays a scientific and economic challenge. Concerning the activated alkenes, the area is still little developed and applications to the synthesis of products (chiral amines) of high commercial values have not yet been reported. In the non-activated alkenes (simple olefins) version, in spite of much effort, no satisfactory results have been achieved yet. We have discovered the first catalytic systems really efficient for this type of reaction, made up from the association of Pt(II), Pt(IV) or Rh(III) salts with phosphonium halides (n-Bu4PX). These are the most performing systems ever reported for the hydroamination of ethylene by weakly basic amines and the only ones allowing the hydroamination of higher olefins. Moreover, the high regioselectivity (95 %) obtained, is favourable for the development of an enantioselective version, which remains an unexplored area of research. We have a triple objective: (a) Arrive at a complete understanding of how the two simple metal systems recently developed in our laboratory operate, by the isolation of intermediates of the catalytic cycles, mechanistic studies, and computational studies. With such knowledge in hand we will be able to design new generation catalytic systems that meet with the requirements of efficient large scale production. (b) Develop the intermolecular enantioselective hydroamination with two independent goals: to find catalytic systems of general applicability for the hydroamination of activated alkenes in order to accomplish efficient syntheses of high added value chiral amines; to accomplish the asymmetric hydroamination of non activated olefins. Ligands already existing in the two participating laboratories have the potential of yielding the first successful demonstration of feasibility. Simple modifications of the ligand environment will subsequently be guided by the acquired knowledge of the key transition state (previous objective) and by QM/MM or full QM calculations. (c) Adapt the experimental conditions in such a way that the catalyst can be efficiently separated from the reaction products, recovered and recycled without significant leaching or decomposition. This objective may also be achieved through ligand modification.

The presence of the fluorine atom in molecules increases their biological activity .This represents a significant interest for applications in medicinal chemistry and agrochemical industries. Given the growing interest to introduce an atom or atom (s) of fluoride in an organic molecule, it is essential to develop new methods for selective fluorination. A new way is the preparation of fluorinated building blocks by nucleophilic aromatic substitution from the chlorinated starting materials in the presence of a catalyst and hydrogen fluoride as the fluorinating agent. The objective of this work is to establish firstly the feasibility of such reactions and secondly the rules determining the operating conditions and the formulation of catalysts. This will thus adapt the catalyst as a function of the reactivity of chlorinated substrates. The project partners are complementary and have a proven ability to work together.