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Bridged silsesquioxanes containing a chiral diphosphine substructure. Catalytic properties in asymmetric hydrogenation

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Abstract

Bridged silsesquioxanes with asymmetric catalytic properties are described. These new silica-based materials are obtained by the sol-gel hydrolysis of an organosilylated chiral compound bearing rhodium-complexed diphosphine ligands. The incorporation of the organometallic species in various hybrid networks was achieved upon co-hydrolysis of the latter silylated ligands with TEOS or with 1,4-bis(trimethoxysilyl)benzene. These amorphous hybrids have been tested as enantioselective catalysts for the hydrogenation of (Z)α-(acetamido)cinnamic acid to the corresponding aminoacid and the results were compared with that obtained from the complexed precursor in homogeneous medium and related grafted silica. Enantioselectivities slightly higher than for homogeneous reaction were obtained in the case of the heterogeneous catalysts prepared by the direct hydrolysis of the rhodium-complexed diphosphine compound or by its co-hydrolysis with 1,4-bis(trimethoxysilyl)benzene. Conversely, a significant decrease in selectivity was observed when the organometallic species was immobilised in silica or grafted at the surface of silica.

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Abbreviations

BTMB:

1,4-Bis(trimethoxysilyl)benzene

TEOS:

Tetraethyl orthosilicate

ee:

Enantiomeric excess

BET:

Brunauer–Emmet–Teller

HPLC:

High pressure liquid chromatography

HPDEC:

High polarisation decoupling

MAS:

Magic angle spinning

CP-MAS:

Cross polarisation-magic angle spinning

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Acknowledgments

This work was supported by the CNRS and by the French Ministry of Research.

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Authors and Affiliations

  1. Laboratoire Architectures Moléculaires et Matériaux Nanostructurés, Institut Charles Gerhardt Montpellier (UMR 5253) CNRS-UM2-ENSCM-UM1, Ecole Nationale Supérieure de Chimie de Montpellier, 8, rue de l’école normale, 34296, Montpellier cedex 5, France

    Anne Brethon, Catherine Bied, Joël J. E. Moreau & Michel Wong Chi Man

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  1. Anne Brethon
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  2. Catherine Bied
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  3. Joël J. E. Moreau
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Correspondence to Michel Wong Chi Man.

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Brethon, A., Bied, C., Moreau, J.J.E. et al. Bridged silsesquioxanes containing a chiral diphosphine substructure. Catalytic properties in asymmetric hydrogenation. J Sol-Gel Sci Technol 50, 141–151 (2009). https://doi.org/10.1007/s10971-009-1919-0

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