Abstract
AbstractTwo different synthetic concepts led to the formation of 17, 19, and 29, the first structural isomeric benzobis[1,3]oxathiins. Hetero‐DielsAlder reactions of diethyl mesoxylate 14 and the open valence isomers of the benzobisthietes 12 and 18 yielded the linear benzobis[1,3]oxathiin 17 and its angular isomer 22, respectively. The isomeric angular system 29 could be obtained by a twofold O,S‐acetalization reaction of the dihydroxydisulfanyl compound 27 and acetone (28).
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