Blanc SIMI 7 - Blanc - SIMI 7 - Chimie moléculaire, organique, de coordination, catalyse et chimie biologique

Flexible Molecular Plateform, a Tool for Catalysis – P2MOC

development of a new family of multitask and polyfunctional ligands

conception of new catalytic tools able to combine several activation modes such as coordination or organic. Theses new tools aim at promoting new transformation sequences and focus onMolecular targets of increasing complexity.

multicatalytic combinations

In a particularly competitive international context, the objectives are to associate several catalytic concepts and/or to generate multiple activations using a unique family of polyfonctional promoters.The general motif of this family includes a pyridine and a pendant methylamine arm. Development of this family of ligands may be beneficial to a more diversified and more (régio-, chimio- énantio-selective metal-based catalysis as well as to the rapidly expanding organocatalysis. The realization of reactions sequences based on this concept represent a coherent major stake with the development of an environment-friendlier chemistry.

Our methodology aims first at strengthening the preliminary results obtained by the consortium in the field of metallic- and organo-catalysis. Secondly, new reactions and combined ransformations will be targeted to illustrate the concept. Applications in the preparation of more complex, bioactive molecules or in the pharmaceutical application will be developed. Several activation modes are envisionned complementing the existing toolbox combining various catalytic systems and reaction sequences. The developed ligands will be then tested by each partner in their own fields of expertise.

A consequent part of work is currently dealing with the preparation of new ligands within the pyridylméthylamines family. First, new stes of ligands have been realised by partners 2 and 3, thta consisted in spreading this family to triaza and tetraaza motifs. The preparation of targets required the development of news( methodologies towrads the synthesis of both dimeric ligands and the adaptation of existing methods allowing the introduction of chiral pendant arms at pyrimidine analogues.
Furthermore, the use of pyridineméthylamines as organo-catalysts has just been successfully carried out in the trifluoroalkylation of indoles. The latter point represents an important advance within this context validating the concept of a unique family of ligands which can play the role of both organo-and metallo catalyst. Theoretical calculations were realized in support to experimental datas.

Several perspectives are envisagedsuch as
- Evaluation of catalytic properties of new ligands prepared in task 1. by all partners
- modification of the pendant arm by introducing an additionnal carbon atom between both nitrogen atoms.
- extension of the Mukaiyama reaction to a phenyloguous version.
- characterization of the complexes combining tetraaza ligands and lanthanides as well as the study of the potential transfer of chiralité on model reactions as hydroaminations.
- structure-activity rationalization on Pd(II) complexes using 15N RMN.

To date, the consortium published preliminary results:
New J. Chem., DOI:10.1039/C3NJ00310H
as well as one invited international conference, one oral presentation and one invited international seminar.

The construction of molecular structures of increasing complexity by controlled assembly of molecular building blocks and/or controlled creation of C-C and C-heteroatom bonds is one of the major challenges of the XXIst century chemistry. In this context, catalysis is a powerful tool that will allow innovations at the heart of social stakes and the “strategie nationale de recherche et d’innovation”. If the emerging developments in catalysis as “combined-catalysis” or the combination of catalytic systems provide new solutions, major scientific constrictions remain to be overcome to generate an increased cooperativity between catalytic systems within the same reaction sequence. The P2MOC project targets the design of new multitask, versatile catalytic systems with multiple and different activation sites within the same catalytic system that will combine the advantages and benefits of each isolated catalyst. The main challenge is the development of a promoter platform based on pyridylmethylamine core. In this context, the development of this family of promoterswill associate multiple criteria such as selectivity, efficiency and creativity but also the general robustness principle. They are likely to activate a substrate or to coordinate a metal in order to carry out a series of reactions organo- and/or metal-catalyzed, sequentially or in tandem. The interest of the targeted pyridylalkylamines family lies in the large number of easily accessible modulations. Thus, apart from the conventional steric modulations by groups of various size (aromatic, aliphatic cyclic or not) and the relative stereochemistry set between the substituents, acidic, basic, chelating or not sites could be modified to allow an on-demand design to the promoter platform. One advantage to the development of N-based bi-(or poly-) functional promoters is that they can overcome the use of two different catalysts, primary amine - secondary amine for example, integrating both functions at the same promoter. The role of each fragment can be modulated and even reversed by moving from the acidic to the basic form of functions present on the platform. Several reactions and/or novel associations of reactions are targeted to illustrate the concept. Thus, the formation of aziridines followed of their uses and opening using the same catalytic system, combinations of a Friedel-Crafts or a Heck reaction with a Henry reaction in the same sequence are proposed examples. The different developed methodologies will be applied to the preparation of complex and bioactive molecules or compounds with potential pharmaceutical application in the indole, diazepine series or biarylic pattern.

Project coordinator

Monsieur Damien PRIM (UNIVERSITE DE VERSAILLES - SAINT-QUENTIN - EN - YVELINES) – prim@chimie.uvsq.fr

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

ILV-UVSQ UNIVERSITE DE VERSAILLES - SAINT-QUENTIN - EN - YVELINES
ICMMO-UPSud UNIVERSITE DE PARIS XI [PARIS- SUD]
ICG-ENSCM ECOLE NATIONALE SUPERIEURE DE CHIMIE DE MONTPELLIER

Help of the ANR 454,995 euros
Beginning and duration of the scientific project: December 2011 - 48 Months

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