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Synthesis 2008(15): 2476-2487  
DOI: 10.1055/s-2008-1067176
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Intramolecular Michael-Type Additions to Vinyl Bissulfoxides: Enantioselective Synthesis of Chiral Aldehydes

Timo Gehringa, Joachim Podlech*a, Alexander Rothenbergerb
a Institut für Organische Chemie, Universität Karlsruhe (TH), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
Fax: +49(721)6087652; e-Mail: joachim.podlech@ioc.uka.de;
b Institut für Anorganische Chemie, Universität Karlsruhe (TH), Engesserstraße 15, 76131 Karlsruhe, Germany
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Publikationsverlauf

Received 5 May 2008
Publikationsdatum:
08. Juli 2008 (online)

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Abstract

The diastereoselective auxiliary-based intramolecular Michael-type additions to alkylidene bissulfoxides derived from dithiane and dithiolane were investigated. Utilization of substrates bearing N- and O-nucleophilic functions led to the formation of the respective cyclic substrates with selectivities ranging from 51:49 to 85:15. Cleavage of the bissulfoxide moiety by a two-step sequence yielded chiral carbaldehydes. The enantiomerically pure compounds obtained by this procedure, for example, tetrahydropyran-2-carbaldehyde and homopipecolic aldehyde, are hardly accessible by other routes. Both enantiomers of the target molecules are available since the stereochemical information is introduced with the readily available diethyl d- and l-tartrates.

Key words

nucleophilic additions - sulfoxides - thioacetals - umpolung - stereoelectronic effects

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CCDC 683981 (19b), CCDC 683980 (20b) and CCDC 683979 (21b) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.