Alkaline earth metals for C–O bond functionalisation – ALCACAT

ALCACAT assembles two complementary teams at University of Rennes 1 (Dr. Y. Sarazin (coordinator), Prof. J.-F. Carpentier, Dr. E. Caytan) and University Paris-Sud in Orsay (Prof. V. Gandon, Dr. C. Bour, Dr. D. Leboeuf). The project revolves around catalyst engineering via coordination chemistry of the large alkaline earths (Ae, with Ae = calcium, strontium and barium) and Csp3–O bond functionalisation in homogeneous catalysis, with a view to producing fine chemicals from a series of key reactions (coupling of alcohols with boronic acids, synthesis of cyclopentenones and pyrroles, total synthesis of santarubin A, and depolymerisation of lignin).

The ambition is to synthesise unusual alkaline earth species, e.g. cationic and hydrido complexes, anticipated to be highly reactive and to implement them in related catalytic procedures where Csp3–O bond activation is a key step to yield valuable chemicals. For the considered catalysed reactions, specific molecular alkaline earth catalysts featuring varying levels of Lewis acidity will also be devised. This will be the convenient and versatile entry point to the catalytic studies to be performed. A multiplicity of original and independent synthetic strategies (all relying on the previous experience of the Rennes partners) is considered for the synthesis of the targeted catalysts, to ensure that the project never comes to a stalemate.

Regarding catalysis, the four considered reactions investigated by the Orsay partners all involving Csp3–O bond functionalisation are highly topical, and likely to lead to marketable products and processes. They will require the specific reactivity of the Ae catalysts with modifiable Lewis acidity. Again, a large set of different catalysts coming from different sources will be implemented to warrant the best chances of success.

Two teams with their specific sets of competences, both essential to the success of ALCACAT, will work in a collaborative and synergetic framework. The Rennes partners have a large experience in catalyst design, including with alkaline earths. The team in Orsay is well-known for its competences in designing original catalysed reactions mediated by main group catalysts.

The hiring of a PhD student (Rennes) and of a post-doc research assistant (Orsay) with an overall financial support of ca. € 380,000 (including overheads) are requested for this 42-month project. Secondments of these hired members of staff in the lab of the other partner will be an integral component of the proposal, to ensure optimal synergy and transfer of competences.