Asymmetric Diethyl‐ and Diphenylzinc Additions to Aldehydes by Using a Fluorine‐Containing Chiral Amino Alcohol: A Striking Temperature Effect on the Enantioselectivity, a Minimal Amino Alcohol Loading, and an Efficient Recycling of the Amino Alcohol
- 18 January 2005
- journal article
- Published by Wiley in Chemistry – A European Journal
- Vol. 11 (3), 945-950
- https://doi.org/10.1002/chem.200400703
Abstract
A chiral pyrrolidinylmethanol derivative containing perfluoro‐ponytails (5) was prepared from (S)‐proline. The use of this perfluoro‐substituted amino alcohol in catalytic asymmetric additions of organozinc reagents to aldehydes affords products with high enantioselectivities in both pure hexane and a mixture of hexane and FC‐72 (perfluorohexane). Enantiomeric excesses up to 94 and 88 % ee have been achieved in Et2Zn and Ph2Zn additions, respectively. For the reactions in the biphasic solvent system a striking temperature effect was observed. Thus, when the temperature was raised from 0 to 40 °C the ee value of the product increased from 81 to 92 %. Furthermore, the catalyst loading could be remarkably low, and with only 0.1 mol % of amino alcohol 5 a product with 90 % ee was obtained in the Et2Zn addition to benzaldehyde in hexane. The perfluoro‐ligand was easily recovered by simple phase separation, and until the ninth repetition its reuse proceeded without significant loss of enantioselectivity and reactivity.Keywords
This publication has 44 references indexed in Scilit:
- Phenyl versus Ethyl Transfer in the Addition of Organozinc Reagents to Aldehydes: A Theoretical StudyAngewandte Chemie International Edition, 2003
- ROMP-Polymers in Asymmetric Catalysis: The Role of the Polymer BackboneAdvanced Synthesis & Catalysis, 2002
- Palladium-catalysed asymmetric allylic alkylation in the presence of a chiral ‘light fluorous’ phosphine ligandChemical Communications, 2001
- A novel ferrocenyl diselenide for the catalytic asymmetric aryl transfer to aldehydesNew Journal of Chemistry, 2000
- Green chemistry development in fluorine scienceJournal of Fluorine Chemistry, 2000
- Perfluorocarbon-soluble catalysts and reagents and the application of FBS (fluorous biphase system) to organic synthesisJournal of Fluorine Chemistry, 1999
- Fluorous Biphase ChemistryAccounts of Chemical Research, 1998
- A General Solid-Phase Synthesis Strategy for the Preparation of 2-Pyrrolidinemethanol LigandsThe Journal of Organic Chemistry, 1995
- Self and Nonself Recognition of Asymmetric Catalysts. Nonlinear Effects in the Amino Alcohol-Promoted Enantioselective Addition of Dialkylzincs to AldehydesJournal of the American Chemical Society, 1995
- Catalytic asymmetric induction. Highly enantioselective addition of dialkylzincs to aldehydes using chiral pyrrolidinylmethanols and their metal saltsJournal of the American Chemical Society, 1987