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

Información del proyecto

Identificador del acuerdo de subvención: INTAS-1999-01541

Proyecto cerrado

Fecha de inicio 1 Mayo 2000

Fecha de finalización 30 Abril 2002

Financiado con arreglo a

• International Association for the promotion of cooperation with scientists from the independent states of the former Soviet Union (INTAS), 1993-

Coste total

Sin datos

Aportación de la UE

€ 89 700,00

Coordinado por

Ecole Nationale Supérieure de Chimie de Paris
France

Objetivo

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?

Programa(s)

• IC-INTAS - International Association for the promotion of cooperation with scientists from the independent states of the former Soviet Union (INTAS), 1993-

Tema(s)

• 3 - Chemistry
• OPEN - OPEN Call

Convocatoria de propuestas

Datos no disponibles

Régimen de financiación

Datos no disponibles

Coordinador

Ecole Nationale Supérieure de Chimie de Paris

• Aportación de la UE: Sin datos
• Dirección: 11 rue P. et M. Curie ; 75231 Paris Cedex 05 ; Francia
• Coste total: Sin datos

Participantes (5)

M.V. Lomonosov Moscow State University

Rusia

• Aportación de la UE: Sin datos
• Dirección: Leninskie Gory ; 119899 Moscow
• Coste total: Sin datos

Russian Academy of Sciences

Rusia

• Aportación de la UE: Sin datos
• Dirección: 141 Prospekt Oktyabrya ; 450075 Ufa
• Coste total: Sin datos

University of Basel

Suiza

• Aportación de la UE: Sin datos
• Dirección: 19 St. Johanns-Ring ; 4056 Basel
• Coste total: Sin datos

Ural Branch of the Russian Academy of Sciences

Rusia

• Aportación de la UE: Sin datos
• Dirección: 48 Pervomajskaja ; 167610 Syktyvkar
• Coste total: Sin datos

Utrecht University

Países Bajos

• Aportación de la UE: Sin datos
• Dirección: 8 Padualaan ; 3584 CH Utrecht
• Coste total: Sin datos