A Stereoselective Access to Dihydroxylated Pyrrolidines by Reductive Ring Contraction of 1,2-Oxazines

Hans-Ulrich Reissig; Kai Homann; Florian Hiller; Reinhold Zimmer

doi:10.1055/s-2007-983802

PAPER

A Stereoselective Access to Dihydroxylated Pyrrolidines by Reductive Ring Contraction of 1,2-Oxazines

Hans-Ulrich Reissig*^a, Kai Homann^b, Florian Hiller^c, Reinhold Zimmer*^a
^a Institut für Chemie und Biochemie, Freie Universität Berlin, Takustraße 3, 14195 Berlin, Germany
Fax: +49(30)83855367; e-Mail: hans.reissig@chemie.fu-berlin.de;
^b Institut für Organische Chemie, Technische Universität Darmstadt, 64287 Darmstadt, Germany
^c Institut für Organische Chemie, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, Germany

Abstract

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Abstract

Protected dihydroxylated 1,2-oxazine derivatives such as rac-4 were converted into tetrahydro-1,2-oxazines rac-7 by employing BH₃·THF for the stereoselective reduction of the C=N bond. Compound 7a underwent a reductive ring contraction on hydrogenation in the presence of palladium on charcoal to provide rac-5 in good yield. Enantiopure 1,2-oxazine derivatives 13 and 14 were prepared using (-)-menthol as chiral auxiliary. Their diastereoselective dihydroxylation and BH₃·THF reduction furnished enantiopure tetrahydro-2H-1,2-oxazine derivatives 17 and 18 in good overall yield. Enantiomers (6R)-18 and (6S)-18 were transformed into the two enantiomeric hydroxylated pyrrolidine derivatives 5 in moderate yield.

Key words

cycloaddition - 1,2-oxazines - pyrrolidines - hydrogenation - ring contraction

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References

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