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Synthesis 2011(14): 2192-2204  
DOI: 10.1055/s-0030-1260084
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

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

Nina A. Nedolya*, Ol’ga A. Tarasova, Ol’ga G. Volostnykh, Alexander I. Albanov, Ludmila V. Klyba, Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry of the Russian Academy of Sciences, Siberian Branch, Favorsky Street 1, 664033 Irkutsk, Russian Federation
Fax: +7(3952)419346; e-Mail: nina@irioch.irk.ru;
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Publikationsverlauf

Received 4 April 2011
Publikationsdatum:
21. Juni 2011 (online)

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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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22

Very recently, we have found (unpublished data) that excluding the purification stage of 1-aza-1,3,4-trienes (column chromatography) and reversing the separation and purification steps for azepines and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.