Enantiomerically pure amino acids are synthesised as starting materials for the synthesis of new chiral 1,2-, 1,3- and 1,4-aminoalcohols. These aminoalcohols are then tested as chiral auxiliaries in enantioselective synthesis. Instead of the aminoalcohols, previously synthesised new phosphorus-containing chiralica are also used. The use of enantiomerically pure aminoalcohols as components of homogeneous catalysts in enantioselective synthesis is being investigated in particular detail. This involves, among other things

(a) the enantioselective reduction of prochiral ketones.

(b) the enantioselective alkylation of aldehydes.

(c) the enantioselective protonation of enolates.

(d) the enantioselective Michael addition.

(e) the enantioselective addition of P-nucleophiles to prochiral imines.

Initial results on the heterogenisation of homogeneous catalysts are promising. The enantioselectivity of the new heterogeneous catalysts obtained in catalytic model reactions is in some cases just as good as when using corresponding amounts of comparable homogeneous catalysts.

Prof. Dr Santiago Luis, University Jaume I, Castellon / Spain

Prof. Dr Jaques Muzart, Université Reims / France

Prof. Dr Masakatsu Shibasaki, University of Tokyo / Japan

Prof. Dr Hiroaki Sasai, Osaka University / Japan

Prof. Dr Byung Tae Cho, Hallym University / South Korea

Prof. Dr Romero Brunet, Universidad Autonoma Madrid / Spain

Prof. Dr Silvian Jugé, Université Cergy Pontoise / France

Prof. Dr Francine Agbossou, Université de Lille / France

M. Kossenjans, M. Soebert, S. Wallbaum, K. Harms, J. Martens, H. G. Aurich: Synthesis of β-amino alcohols and thiols with 2-azabicyclo[3.3.0]octane backbone and their application in enantioselective catalysis, J. Chem. Soc. Perkin I 1999, 2353-2366. (DOI:10.1039/a902362c)

O. Juanes, J. C. Rodríguez-Ubis, E. Brunet M. Kossenjans, H. Pennemann, J. Martens: New chiral catalysts containing N,O-heterocycles derived from chiral amino alcohols, Eur. J. Org. Chem. 1999, 3323-3333. (DOI:10.1002/(SICI)1099-0690(199912)1999:12<3323::AID-EJOC3323>3.0.CO;2-W)

J. Wilken, S. Erny, S. Wassmann, J. Martens: New C₂-symmetric 2,4-bis(1-hydroxycyclopentyl)azetidines derived from(S)-1-phenylethylamine and their application in the enantioselective catalysis, Tetrahedron: Asymmetry 2000, 11, 2143-2148. (DOI:10.1016/S0957-4166(00)00155-5)

I. Schlemminger, Y. Saida, H. Gröger, W. Maison, N. Durot, H. Sasai, M. Shibasaki, J. Martens: Concept of Rigidity: How to Make Enantioselective Hydrophosphonylation of Cyclic Imines Catalyzed by Chiral Heterobimetallic Lanthanoid Complexes almost Perfect, J. Org. Chem. 2000, 65, 4818-4825. (DOI:10.1021/jo991882r)

I. Schlemminger, A. Lützen, A. Willecke, W. Maison, R. Koch, W. Saak, J. Martens: Highly Diastereoselective Hydrophosphonylation of Cyclic Imines using BINOL as Source of Chirality, Tetrahedron Lett. 2000, 41, 7285-7288. (DOI:10.1016/S0040-4039(00)01265-X)

C. Pasquier, S. Naili, A. Mortreux, F. Agbossou, L. Pélinski, J. Brocard, J. Eilers, I. Reiners, V. Peper, J. Martens: Free and Cr(CO)₃-Complexed Aminophosphine Phosphinite Ligands for Highly Enantioselective Hydrogenation of α-Functionalised Ketones, Organometallics 2000, 19, 5723-5732. (DOI:10.1021/om0006312)

J. Wilken, M. Winter, I. Stahl, J. Martens: Catalytic enantioselective addition of diethylzinc to 1,3-dithian-2-yl substituted aliphatic aldehydes: a new approach to optically active 2-(hydroxyalkyl)-1,3-dithianes, Tetrahedron: Asymmetry 2000, 11, 1067-1071. (DOI:10.1016/S0957-4166(00)00029-X)

N. Graf von Keyserlingk, J. Martens: Synthesis of optically active functionalised cyclic ketimines and their application in enantioselective catalysis, Tetrahedron: Asymmetry 2001, 12, 2213-2222. (DOI:10.1016/S0957-4166(01)00379-2)

M. I. Burguete, E. García-Verdugo, M. J. Vicent, S. V. Luis, H. Pennemann, N. Graf von Keyserlingk, J. Martens: New Supported β-Amino Alcohols as Efficient Catalysts for the Enantioselective Addition of Diethylzinc to Benzaldehyde under Flow Conditions, Org. Lett. 2002, 4, 3947-3950. (DOI:10.1021/ol026805o)

M. I. Burguete, M. Collado, E. García-Verdugo, M. J. Vicent, S. V. Luis, H. Pennemann, N. Graf von Keyserlingk, J. Martens: Development of small focused libraries of supported amino alcohols as an efficient strategy for the optimisation of enantioselective heterogeneous catalysts for the ZnEt₂ addition to benzaldehyde, Tetrahedron 2003, 59, 1797-1804. (DOI:10.1016/S0040-4020(03)00071-1)

S. V. Luis, B. Altava, M. I. Burguete, M. Collado, J. Escorihuela, E. Garcia-Verdugo, M. J. Vicent, J. Martens: Preparation and Optimisation of Polymer-Supported and Amino Alcohol Based Enantioselective Reagents and Catalysts, Ind. Eng. Chem. Res. 2003, 42, 5977-5982 (DOI:10.1021/ie030150t).