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–catalyst ion pair in this reaction, as well as the crucial role of the presence of water to achieve high enantioselectivities.

Organocatalytic Asymmetric Mannich Reactions with N-Boc and N-Cbz Protected alfa-Amido Sulfones (Boc: tert-Butoxycarbonyl, CBz: Benzyloxycarbonyl) / Marianacci, Olindo; Micheletti, Gabriele; Bernardi, Luca; FINI, Francesco; Fochi, Mariafrancesca; Pettersen, Daniel; Sgarzani, Valentina; Ricci, Alfredo. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - STAMPA. - 13:29(2007), pp. 8338-8351. [10.1002/chem.200700908]

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

FINI, Francesco;
2007

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–catalyst ion pair in this reaction, as well as the crucial role of the presence of water to achieve high enantioselectivities.
20-ago-2007
13
29
8338
8351
Organocatalytic Asymmetric Mannich Reactions with N-Boc and N-Cbz Protected alfa-Amido Sulfones (Boc: tert-Butoxycarbonyl, CBz: Benzyloxycarbonyl) / Marianacci, Olindo; Micheletti, Gabriele; Bernardi, Luca; FINI, Francesco; Fochi, Mariafrancesca; Pettersen, Daniel; Sgarzani, Valentina; Ricci, Alfredo. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - STAMPA. - 13:29(2007), pp. 8338-8351. [10.1002/chem.200700908]
Marianacci, Olindo; Micheletti, Gabriele; Bernardi, Luca; FINI, Francesco; Fochi, Mariafrancesca; Pettersen, Daniel; Sgarzani, Valentina; Ricci, Alfredo
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11380/1122079
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