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Synthesis 1997; 1997(2): 183-190
DOI: 10.1055/s-1997-1156
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Highly Diastereoselective, Nucleophilic Alkenoylation of Enantiopure α-Oxy- and α-Aminoalkanals by Lithiated [1-(p-Toluenesulfonyl)alk-2-enyl] Carbamates. Revision of the Stereochemistry and Application to the Synthesis of a Dihydroxyethylene Dipeptide Isostere

Dieter Hoppe1 , Petra Tebben2 , Michael Reggelin3 , Michael Bolte4
  • 1Organisch-Chemisches Institut der Universität Münster, Corrensstraße 40, D-48149 Münster, Germany, Fax +49(251)8339772
  • 2Institut für Orgainsche Chemie der Universität Kiel, Olshausenstraße 40-60, D-24118 Kiel, Germany
  • 3Institut für Orgainsche Chemie der Universität Kiel, Olshausenstraße 40-60, D-24118 Kiel, Germany; Institut für Organische Chemie der Universität Frankfurt, Marie-Curie-Straße 11, D-60439 Frankfurt/M, Germany
  • 4Institut für Organische Chemie der Universität Frankfurt, Marie-Curie-Straße 11, D-60439 Frankfurt/M, Germany
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Publication History

Publication Date:
31 December 2000 (online)

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The addition of lithiated [1-(p-toluenesulfonyl)alk-2-enyl] carbamates to α-stereogenic aldehydes proceeds with steric approach control according to the Felkin-Anh model to produce α‘-carbamoyloxy-α,β-enones by carbonyl migration and elimination of p-toluenesulfinate. Conversion of two enones to 1,3-dioxan-2-one 9 and to (2S,3S,4S,5S)-methyl-5-(dibenzylamino)-4-(N,N-diisopropylcarbamoyloxy)-3-hydroxy-2-isopropyl-7-methyloctanoate (16a), respectively, furnished samples suitable for X-ray crystal structure analyses to confirm the stereochemical course of the addition step.

nucleophilic alkenoylation - lithiated allyl carbamates - lithiated allyl sulfones