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Content archived on 2022-12-23

A new generation of stereoselectors for metal complex catalysis

Objective

The present project aims at gaining new fundamental knowledge in enantioselective catalysis and co-ordination chemistry. Particular attention will be paid to the synthesis and application in homogeneous enantioselective catalysis of pioneering optically active phosphite ligands possessing stereogenic phosphorus atoms. This promising class of phosphorus ligands has been only fragmentary investigated so far, despite their P-chiral phosphine analogues represent well-established highly efficient ligands. Lack of convenient methods for the synthesis of P-chiral phosphites hinders further progress of this ligand group.

Therefore, universal synthetic methods for their preparation from readily available chiral precursors is planned to be developed. Interaction of the novel P*-, P*,N- and P*,P*-ligands with common catalytic precursors (in particular Rh(I), Ir(I), Pd(II) and Pd(0) complexes) will be thoroughly investigated in order to reveal main complexation patterns and create a general model of their co-ordination behaviour. Simultaneously, the novel ligands will be applied in enantioselective hydrogenation of C=C and C=N bonds (Rh, Ir), allylic substitution and tandem allylation (Pd), hydroformylation (Rh) and conjugated addition of R2Zn and R3Al to enones (Cu).

Close integration of co-ordination and catalytic experiments is expected to result in deep insight into the vitally important "ligand's structure - complexation mode - structure of the metal complex - catalytic outcome" correlations. Thanks to the pronounced versatility of chiral phosphites, high conversion and improvement of enantioselectivity up to >90% ee in the listed above catalytic processes are achievable tasks. The most efficient cationic complexes will be immobilised by ion-exchange on a sulfonated hyper-cross-linked polystyrene (unusual sponge-type polymer with unique properties) to obtain easily recyclable catalysts (>3 cycles without loss in activity and enantioselectivity).

As an independent approach to reusable transition metal catalytic systems, conducting of reactions in ionic liquids followed by extraction of the products with non-polar solvents is suggested. Moreover, synthesis of previously not adequately explored optically active ionic liquids and their application as chiral promoters is planned. Potential practically valuable results include development of efficient catalytic synthesis of versatile chiral building blocks, e.g. allyl amines and substituted morpholine heterocycles.

Also, our plans include convenient pathway to a key intermediate for the synthesis of Ibuprofen and pharmaceutically interesting optically active 1-arylethylphosphonates, e.g. a phosphorus analogue of Naproxen. The line of participating teams was thoroughly selected to provide deep experience and state-of-the-art equipment in all the required fields. Combined efforts of the participating world-class groups will have a synergetic effect and lift a joint research up to a principally higher level.

Topic(s)

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Call for proposal

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Funding Scheme

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Coordinator

LEIBNIZ-INSTITUT FÜR ORGANISCHE KATALYSE
EU contribution
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Address
ALBERT EINSTEIN STRASSE, 29A
ROSTOCK
Germany

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Total cost
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Participants (5)