Objective
The objective of this project is to develop a new simple strategy of synthesis of polyazamacrocyclic ligands and their complexes, which possess potential industrial and medical importance using methodology of palladium-catalysed reactions of Csp2-C and Csp2-N bonds formation. The main challenge is to develop a new methodology of the synthesis of different types of ligands with cofacial geometry of two macrocycles, e.g. biscyclam, porphyrin and cyclam, bisporphyrin. This approach opens a new powerful synthetic way to widely used cofacial metalloporphyrins and new types of strapped complexes bearing cyclam and porphyrin or two cyclam fragments bridged by rigid aromatic spacer (anthracene, biphenylene).
As a part of this research proper conditions for arylation of linear and cyclic polyazaalkane ligands will be found and used for the synthesis of unknown N-aryl substituted ligands. The presence of several nitrogen atoms in polyamines may result in the formation of stable complexes, which can suppress catalytic activity of palladium. We'll try to solve the problem of arylation at N-atom by several independent ways. Firstly by testing known catalytic system of arylation in cyclam series and secondary by the elaboration of new more effective catalytic systems for the formation Csp2-N bond using different ligands. The reaction of cyclam with dihalogen derivatives of anthracene and biphenylene in the presence of Pd-catalysts will also be studied.
This reaction can be used for synthesis of desirable ligands with cofacial geometry of two macrocycles. If we fail to make direct arylation of cyclam, stepwise method will be applied for preparation of N-aryl substituted cyclam derivatives.
The cross-coupling reactions of Csp2-C bond formation will be applied to modify the porphyrins using chiral and achiral metallocene compounds and to synthesis of cofacial complexes having two porphyrin rings. It seems possible in this way to synthesize new Pacman porphyrins ligands in few steps instead of 23 steps.
The complexes of new ligands with different metals will be obtained and their structure, properties and possible application will be investigated.
Topic(s)
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21100 Dijon
France