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Synthesis 2008(21): 3397-3406  
DOI: 10.1055/s-0028-1083188
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Superelectrophilic Intermediates in the Synthesis of Novel Indenole Derivatives via 1,5-Cyclization Reactions of 5-Aryl-1-azapenta-1,4-dien-3-ones

Nugzar Ghavtadze, Roland Fröhlich, Klaus Bergander, Ernst-Ulrich Würthwein*
Organisch-Chemisches Institut, Universität Münster, Corrensstr. 40, 48149 Münster, Germany
Fax: +49(251)8339772; e-Mail: wurthwe@uni-muenster.de;
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Publikationsverlauf

Received 19 May 2008
Publikationsdatum:
16. Oktober 2008 (online)

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Abstract

Oximes of 5,5-disubstituted 1-azapenta-1,4-dien-3-ones 3 underwent 1,5-cyclization reactions yielding indenole derivatives 4 in moderate to good yields upon treatment with an excess of tri­fluoromethanesulfonic acid. Similarly, the hydrazone 3g led to indenole 4f upon protonation. The reaction could also be successfully applied to the synthesis of benzo[b]cyclopenta[d]thiophene 5 starting from 3f. Products of a competing aza-Nazarov reaction were not observed. The reaction mechanism is explained by assuming the involvement of dicationic intermediates, generated by superelectrophilic solvation, similar to that of known Nazarov and aza-Nazarov-type transformations. Quantum chemical calculations of reaction energies and activation barriers are discussed with respect to the experimental results.

Key words

cyclization - carbocations - penta-1,4-dien-3-ones - indenoles - quantum chemical calculations

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12

Data sets were collected with a Nonius KappaCCD diffractometer, equipped with a rotating anode generator. Programs used: data collection COLLECT;¹³ data reduction Denzo-SMN,¹4 absorption correction SORTAV,¹5 Denzo,¹6 structure solution SHELXS-97,¹7 structure refinement SHELXL-97,¹8 and graphics SCHAKAL.¹9 CCDC numbers 688078-688079 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK, fax: +44(1223) 336 033, E-mail: deposit@ccdc.cam.ac.uk].