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DOI: 10.1055/s-0030-1260084
Reactions of Lithiated Alkynes and Allenes with Isothiocyanates: A Simple and Efficient Synthesis of New Aryl- or Hetaryl-Substituted 3H-Azepines and 4,5-Dihydro-3H-azepines
Publication History
Publication Date:
21 June 2011 (online)

Abstract
A novel synthetic approach to the preparation of a wide range of 3H-azepines and 4,5-dihydro-3H-azepines bearing various aryl, hetaryl, alkyl, and heteroalkyl substituents from readily accessible starting materials (aryl- and hetaryl-substituted alkynes or allenes, sec-alkyl isothiocyanates, and alkyl halides) has been developed. The methodology is based on a fast and smooth conversion of conjugated 2-aza-1,3,5-trienes derived from 1-aza-1,3,4-trienes, S-alkylated adducts of isopropyl isothiocyanate and allenic or acetylenic carbanions, into seven-membered azaheterocycles, 3H-azepines and 4,5-dihydro-3H-azepines, using potassium tert-butoxide (THF-DMSO, ca. -30 ˚C, 30 min). The ratio of the heterocycles depends on the nature of the substituent on the allene or alkyne and on the 2-aza-1,3,5-triene derived therefrom.
Key words
3H-azepines - 4,5-dihydro-3H-azepines - azatrienes - allenes - alkynes - isothiocyanate - metalation - electrocyclization
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References
Very recently, we have found (unpublished data) that excluding the purification stage of 1-aza-1,3,4-trienes (column chromatography) and reversing the separation and purification steps for azepines and dihydroazepines simplify the reaction product separation and significantly increase their yields.