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

Timo Gehring; Joachim Podlech; Alexander Rothenberger

doi:10.1055/s-2008-1067176

FEATUREARTICLE

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

Timo Gehring^a, Joachim Podlech*^a, Alexander Rothenberger^b
^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

Abstract

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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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