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Synthesis 2002(14): 1945-1952
DOI: 10.1055/s-2002-34368
PAPER
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Michael Addition of Chiral Lithiated Sulfonates to Nitroalkenes: Diastereo- and Enantioselective Synthesis of α,β-Disubstituted γ-Nitro and β-Alkoxycarbonyl Methyl Sulfonates

Dieter Enders*a, Otto Mathias Bernerb, Nicola Vignolaa, Wacharee Harnyinga
a Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Str. 1, 52074 Aachen, Germany
Fax: +49(241)8092127; e-Mail: enders@rwth-aachen.de;
b Kemira Fine Chemicals Oy, P.O. Box 44, 02271 Espoo, Finland
Fax: +358(10)862 2000; e-Mail: mathias.berner@kemira.com;
Further Information

Publication History

Received 15 July 2002
Publication Date:
26 September 2002 (online)

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Abstract

The diastereoselective Michael addition of lithiated enantiopure sulfonates to nitroalkenes is described. High asymmetric inductions were obtained by using 1,2:5,6-di-O-isopropylidene-α-d-allofuranose as a cheap and easily available chiral auxiliary. Racemization-free cleavage of the auxiliary led to α,β-disubstituted γ-nitro methyl sulfonates. A change of the cleavage conditions resulted in α,β-disubstituted β-alkoxycarbonyl sulfonates via the Meyer reaction (de ≥ 98%, ee ≥ 98%).

Key words

Michael additions - nitroalkenes - sulfonates - chiral auxiliaries - carbohydrates - Meyer reaction

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The experimental data will be reported in a separate full paper on the α-alkylations.