Institut de Chimie Moléculaire et des Matériaux d'Orsay

Laboratoire de Catalyse Moléculaire - LCM

Asymmetric Homogeneous and Heterogeneous Catalysis

Coordinator: Emmanuelle Schulz (DR CNRS)

Enantioselective Hydroamination

Jérôme Hannedouche (CNRS Research Fellow), Emmanuelle Schulz (CNRS Research Fellow), Stéphane Germain (PhD student))

Objectives : we aim at finding simple and efficient synthetic methods towards the preparation of asymmetric organometallic catalysts, based on rare earth or alkali metals, active for the catalytic and enantioselective formation of C-N bonds by simple addition of a N-H group on an olefin. Special attention is paid to the catalyst structure determination and to broadening the scope to the enantioselective synthesis of nitrogen cyclic derivatives with high value.

Recent results : these last two years the team developed the synthesis of chiral yttrium amido alkyl ate complexes which proved to be particularly efficient in terms of both activity and enantioselectivity for the asymmetric cyclization of sterically hindered aminoolefins. We have also described the first intramolecular asymmetric hydroamination reaction leading to the formation of enantioenriched quaternary centers.

See :
“Well-defined and easily accessible yttrium complexes for enantioselective cyclisation of amines tethered to 1,2-di-substituted alkenes” Y.  -Chapurina, J. Hannedouche, J. Collin, R. Guillot, E. Schulz, A. Trifonov, Chem. Commun. 2010, 46, 6918-6920.

“Simple chiral diaminobinaphthyl dilithium salts for intramolecular catalytic asymmetric hydroamination of amino-1,3-dienes” - J. Deschamp, C. Olier, E. Schulz, R. Guillot, J. Hannedouche, J. Collin, Adv. Synth. Catal. 2010, 352,2171-2176.

“Enantioselective Intramolecular Hydroamination of Secondary Amines Catalyzed by Easily Accessible Ate and Neutral Rare-Earth Complexes” - C. Queffelec, F. Boeda, A. Pouilhès, A. Meddour, C. Kouklovsky, J. Hannedouche, J. Collin, E. Schulz, ChemCatChem. 2011, 3,122-126.

“Catalytic, enantioselective intramolecular hydroamination of primary amines tethered to di- and tri-substituted alkenes” - Y. Chapurina, H. Ibrahim, R. Guillot, E. Kolodziej, J. Collin, A. Trifonov, E. Schulz, J. Hannedouche, J. Org. Chem. 2011, 76, 10163-10172.

Chiral Rare Earth-based Catalysts

Chiral Lithium-based Catalysts

Keywords: asymmetric catalysis, organometallic complexes, lanthanides, lithium, nitrogen-containing heterocycles, C-N bond formation