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Organocatalytic Asymmetric Mannich Reactions with N-Boc and N-Cbz Protected alfa-Amido Sulfones (Boc: tert-Butoxycarbonyl, CBz: Benzyloxycarbonyl)

By Olindo Marianacci, Gabriele Micheletti, Luca Bernardi, Francesco FINI, Mariafrancesca Fochi, Daniel Pettersen, Valentina Sgarzani and Alfredo Ricci

Abstract

Different malonates and beta-ketoesters can react with N-tert-butoxycarbonyl- (N-Boc) and N-benzyloxycarbonyl- (N-Cbz) protected alpha-amido sulfones in an organocatalytic asymmetric Mannich-type reaction. The reaction makes use of a simple and easily obtained phase-transfer catalyst and proceeds under very mild and user-friendly conditions. The optimised protocol avoids the preparation and the isolation of the relatively unstable N-Boc and N-Cbz imines that are generated in situ from the bench-stable alpha-amido sulfones. The corresponding Mannich bases are generally obtained in good yields and enantioselectivities, and can be readily transformed into key compounds, such as optically active beta3-amino acids in one easy step. Enantioenriched N-Boc and N-Cbz protected beta3-amino acids that are suitable for peptide synthesis are also available from the Mannich adducts through simple manipulations. Control experiments showed the dual role of the enolate\u2013catalyst ion pair in this reaction, as well as the crucial role of the presence of water to achieve high enantioselectivities

Publisher: 'Wiley'
Year: 2007
DOI identifier: 10.1002/chem.200700908
OAI identifier: oai:iris.unimore.it:11380/1122079
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