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

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.

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

References

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We thank the referee for drawing our attention to this mechanism.

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