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Synthesis 2010(8): 1344-1348  
DOI: 10.1055/s-0029-1218658
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Acid-Induced Rearrangement Reactions of α-Hydroxy-1,3-dithianes

Karsten Krohn*, Stephan Cludius-Brandt
Department Chemie, Universität Paderborn, Warburger Str. 100, 33098 Paderborn, Germany
Fax: +49(5251)603245; e-Mail: k.krohn@uni-paderborn.de;
Further Information

Publication History

Received 3 October 2009
Publication Date:
29 January 2010 (online)

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Abstract

Secondary benzylic or aliphatic α-hydroxydithianes 1a-c rearrange to α-thioketones when treated with acid. Related tertiary alcohols 1d-g eliminate to dithioketene ketals (e.g., 2d), which are ring-opened to thiols in some cases (1e, 1f). Allylic α-hydroxydithianes 1h and 1i form the thioesters 2h and 2i (homologation), and the tertiary alcohols 1j and 1k undergo deoxygenation to 2j and 2k.

Key words

1,3-dithianes - dithioacetals - 1,3-dithian-1-oxides - rearrangement - deoxygenation - homologation

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