CE07 - Chimie moléculaire

Preparation of Phospha-cycles based on Metal-Ligand / Photoredox Multi-Cooperative catalysis – MLC-PhotoPhos

Submission summary

The overarching objective of this proposal is the development of innovative catalytic methodologies for P-C bond formation, and in particular for the challenging preparation of P-heterocycles, compounds in demand by the scientific community for optoelectronic, catalysis or pharmaceutical applications. Yet, methodologies for their preparation lack of generality. Here, we propose to take profit the considerable reactivity boost provided by MLC catalysis for the preparation of P-heterocycles, and more precisely for the creation of C-P bonds via the addition of P(O)-H bonds across CC triple bonds. The properties of the targeted MLC catalyst, such as the Brönsted basicity of the pincer backbone, as well as, the Lewis acidity of the metal centre, will be tuned by varying the structure of the ligand precursors (substituents, scaffold, donor groups) and the metal (Ni, Pd, Pt). This work will in addition lead to the expansion the scope of MLC catalysis with G10 metals, much less developed than with TM from G7-9.
Moreover, the development of new strategies for the synthesis of P-heterocycles is an ideal case study to investigate a new dual catalytic approach associating MLC with Photoredox catalysis. This multicatalytic approach combines p-activation of CC triple bond by an electrophilic metal with the activation of the P(O)-H bond by the PC* in association with the basic ligand backbone. Feasibility of the Dual PC-MLC Catalysis will be explored from a mechanistic point of view thanks to thorough physical organic studies of the substrates and the pincer complexes. This will include characterisation of the ground and excited states, and investigation of possible interactions between excited state of the photocatalyst and substrates as well as pincer complexes. Demonstration of the proof of concept of this unprecedented strategy will open an avenue to the activation of other protic functions whose pKa make activation solely by the MLC catalyst unlikely.
An additional target of the project is the development of sustainable synthetic methodologies towards P-containing substrates. They start from hypophosphorous acid (HPA) and thus bypass the generally used PCl3, an energy demanding and waste producing starting material

Project coordination

Blanca Martin Vaca (LABORATOIRE HETEROCHIMIE FONDAMENTALE ET APPLIQUEE - LBPB)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

LHFA - LBPB LABORATOIRE HETEROCHIMIE FONDAMENTALE ET APPLIQUEE - LBPB
LHFA - COP LABORATOIRE HETEROCHIMIE FONDAMENTALE ET APPLIQUEE - COP

Help of the ANR 386,100 euros
Beginning and duration of the scientific project: December 2020 - 48 Months

Useful links

Explorez notre base de projets financés

 

 

ANR makes available its datasets on funded projects, click here to find more.

Sign up for the latest news:
Subscribe to our newsletter