Rearrangements of bridged diallenes. A facile synthesis of novel condensed heterocycles by tandem [3,3]-sigmatropic rearrangement and double intramolecular michael addition of diallenyl disulfides and diselenides. Isolation of stable diallenyl diselenides

Samuel Braverman, Meir Freund

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Abstract

Thienothiophene 14 and selenoloselenophene 16 have been synthesized by the action of lithium methoxide on τ,τ-dimethylallenyl thiocyanate and selenocyanate, respectively. A multistep mechanism involving bis-τ,τ-dimethylallenyl disulfide (20) or diselenide as key intermediates, is suggested. The latter are believed to undergo consecutive 3,3]-sigmatropic rearrangement and double Michael addition, to the observed products. This mechanism is supported by the isolation of bis-τ,τ- diisopropylallenyl and bis-τ-methyl-τ-isopropylallenyl diselenides, under the same reaction conditions, and the rearrangement of the latter to the expected selenoloseleophene 33. The synthesis of the novel mixed selenolothiophene 35 by treatment of a mixture of allenyl thiocyanate 13 and selenocyanate 15 with lithium methoxide, is also described.

Original languageEnglish
Pages (from-to)5759-5776
Number of pages18
JournalTetrahedron
Volume46
Issue number16
DOIs
StatePublished - 1990

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