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Pure Appl. Chem., 2006, Vol. 78, No. 2, pp. 321-331

3-Aminopyrrolidine lithium amides as chiral ligands for alkyllithium derivatives: Synthesis, NMR analysis, and computational study of their mixed aggregates

Anne Harrison-Marchand1, Jean-Yves Valnot1, Aline Corruble1, Nicolas Duguet1, Hassan Oulyadi2, Stéphanie Desjardins2, Catherine Fressigné1,3 and Jacques Maddaluno1

1 Laboratoire des Fonctions Azotées et Oxygénées Complexes, IRCOF,UMR 6014 CNRS, Université de Rouen, 76821 Mont Saint-Aignan Cédex, France
2 Laboratoire de Chimie Organique et Biologique Structurale, IRCOF,UMR 6014 CNRS, Université de Rouen, 76821 Mont Saint-Aignan Cédex, France
3 Laboratoire de Chimie Théorique, UMR 7616 CNRS, Université Pierre and Marie Curie, 4 place Jussieu, 75252 Paris Cédex 05, France

Abstract: An overview of the role of 3-aminopyrrolidine lithium amides (3-APLi's) as chiral ligands for alkyllithiums (AlkLi's) is presented. Synthetic developments as well as NMR characterizations and computational interpretations have been simultaneously and complementarily conducted to improve the ligand design for a model reaction that is the condensation of AlkLi's on o-tolualdehyde, for which enantiomeric excesses up to 80 % were obtained. This study describes the whole chain going from the synthesis of the chiral 3-aminopyrrolidines (3-APs) (18 different 3-APs synthesized) to the characterization of the noncovalent mixed aggregates resulting from the interaction between the organolithium partners (3-APLi:AlkLi). Finally, the docking of the aldehyde on one lithium of the aggregate was analyzed by theoretical means on simplified models, in an attempt to understand the structure of the fully loaded pretransition complexes.