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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