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DOI: 10.1055/s-0034-1379976
Preparation of Tetrahydrothienoazocinone Derivatives
Publication History
Received: 19 November 2014
Accepted after revision: 15 December 2014
Publication Date:
26 January 2015 (online)
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Abstract
Three regioisomeric thieno[c]azocine derivatives were prepared in six steps from bromothiophene carboxylic acids. The reaction sequence started with an esterification with isopropyl alcohol. The resulting esters were submitted to a Heck reaction with tert-butyl acrylate followed by catalytic hydrogenation. Subsequent Dieckmann condensation gave cyclopentathiophenes with a cyclic β-oxo ester motif, which were α-alkylated with phenacyl bromide to furnish 1,4-diketones. The latter were converted in the key step, a bismuth-catalyzed ring transformation with methylamine, yielding the racemic eight-membered ring lactams, that is, tetrahydrothieno[2,3-c]-, [3,2-c]-, and -[3,4-c]azocine derivatives in overall yields of 25%, 16% and 12%, respectively.
Key words
ring expansion - heterocycles - medium-ring compounds - lactams - thiophene derivatives - azocine derivativesSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1379976.
- Supporting Information
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