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New Approaches to catalytic asymmetric addition to unsaturated bonds using chiral H-donors and Chiral Transition-Metal Catalysts

Obiettivo

Fundamental problem to be solved in the course of the project implementation is to find out regularities in asymmetric addition (molecular hydrogen, organoaluminum compounds, carbanions) to C=C bond and asymmetric addition to C=O bond (hydrogen transfer, trimethylsilylcyanide, carbanions) in prochiral vinyl- and a-, b-, and g-ketophosphonic esters and comparison of the results with other prochiral organic molecules, using new catalytic systems - homogeneous and immobilized Ru, Rh, Ir and Pd complexes. The novelty of the project is that Double Asymmetric Induction, H-transfer from cheap naturally occurred chiral compounds and wide use of organoaluminum compounds will be investigated for the first time in these processes to increase reaction enantioselectivity.

Several of the most promising classes of chiral catalysts and reagents, such as
i) easily prepared in situ chiral ruthenium(II) catalysts with organophosphorus ligands derived from atropoisomers of binaphtyls and biphenyls;
ii) transition metal chiral catalyst with chiral ligands derived from aminophosphines and semicorrins, based on bis(oxazolines), pyrrollidines, phosphinooxazolynes and similar five-member azaheterocycles;
iii) catalysts with polyphosphine ligands (four and more phosphorus atoms in molecule), derived for example from tetrakis(diphenylphosphinomethylene)tolane, which presents intermediate step to dendrimeric organophosphorus ligands;
iv) chiral organoaluminum compounds as reagents for catalytic reduction.

The final report should contain the answers on three main questions:
1) Does the combined application of chiral catalysts and chiral reagents provide significant increase in optical yield of final compound? Is it reasonable from synthetic and economic point of view to use Double Asymmetric Induction as described above for chiral synthesis?
2) How naturally occurring alcohols and hydroxyacids can be employed for chiral reduction by H-transfer to prochiral ketophosphonates, other ketones and their oximes?
How to receive high degrees of conversion and enantiomeric yields of final compounds?
3) Is it possible and how to employ chiral organoaluminium compounds for asymmetric reduction of C=C and C=O bonds?

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Coordinatore

Ecole Nationale Supérieure de Chimie de Paris
Contributo UE
Nessun dato
Indirizzo
11 rue P. et M. Curie
75231 Paris Cedex 05
Francia

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