Au-MLC · Cooperative Au catalysis with chemically non-innocent ligands.
Horizon 2020 — Marie Skłodowska-Curie Actions
- Duration
- 2019-08-01 → 2021-07-31
- EU contribution
- €184,708
- Participants
- 1
- Scheme
- MSCA-IF-EF-ST
Lines connect the coordinator with its partners.
Results in brief
Cooperative Au catalysis with chemically non-innocent ligands.
Homogeneous catalysis represents one of the most powerful set of tools for organic synthesis, on the industrial scale as well as on the laboratory one; in this field, homogeneous gold catalysis has seen an exponential growth of interest in the last quarter century, and is nowadays one of the most lively field of research, given its relative novelty, its positioning in the intersection between synthetic chemistry and organometallic chemistry, and its unique properties; in particular, the investigation of Au(III) species has been widely overlooked by the community, and represents today a source of ground-breaking development. Much in the same way, Metal-Ligand-Cooperation (MLC) is a relatively young field of research, yet has provided tremendous improvement in the efficiency of known catalytic methods, as well as disclosing new, unexpected reaction patterns. MLC strategies have been applied only scarcely to gold chemistry, and exclusively to Au(I) catalysts; the discovery of MLC-competent Au(III) species would represent a paramount breakthrough, granting advancement in many of the fields of research on gold chemistry. The Au-MLC project aimed at elaborating a library of well-defined Au(III) complexes with MLC characteristics, taking advantage of their rich behaviour to gain insight on their fundamental properties, as well as on their catalytic aptness. The action succeeded in the development of Au(III) complexes with MLC properties, although their catalytic applications were not achieved. During the development of the project, we also found that their synthesis involve a novel, base-triggered oxidative addition to Au(I), which represents a fascinating discovery on its own, given the interest that the oxidative addition to gold has attracted in recent times. We therefore devoted much effort to the comprehension of the process, providing new insights that will be valuable for both fundamental applied (catalytic) developments of gold chemistry.
Data: CORDIS, © European Union
Project objective
Gold catalysis has gathered increasing attention from the synthetic community during the last decades, due to the remarkable ability of Au centres to promote chemical transformations. Typically, gold catalysis is based on its peculiar properties as a Lewis acid, that make it very well suited for the activation of unsaturated bonds. On the other hand, the use of gold in more sophisticated processes, such as cooperative catalysis, is at its pioneering stage, and only few examples of these strategies are currently known. Metal-Ligand Cooperation strategies (MLC) are an emerging tool in homogeneous catalysis, based on the interplay between the metal centre and the non-innocent (bifunctional) ligand. This synergy vastly enhances the performances of known transformations, and even enables new sets of reactivities. MLC has been applied to many metal centres, often with spectacular results; Au-MLC strategies, however, are unknown to date. This project focuses on the development of a family of novel Au(III) complexes bearing Brønsted basic, non-innocent pincer ligands characteristics. Their fundamental study will be performed, assessing their Lewis acidity (especially in the Pearson HSAB scale), their Brønsted basicity, and their stoichiometric interaction with X–H bonds. Based on these results, their use as bifunctional Lewis-acid catalysts will be explored for the electrophilic activation of alkynes, carbonyl compounds, and alcohols. The design and development of sequential reactions involving the bifunctional gold catalysts obtained in the context of this project will be the ultimate, most ambitious goal of this action.
Original text from CORDIS.
Participants
- CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE CNRS · ParisCoordinatorFrance
Links
Data: CORDIS, © European Union