Issue 10, 2011
From the journal:

Organic & Biomolecular Chemistry

An efficient approach to azirino and pyrrolo-fused dibenzazepines. Conformations of substituted dibenzo[c,f]pyrrolo[1,2-a]azepines†‡

Alexander F. Khlebnikov,*a   Mikhail S. Novikov,a   Maria V. Golovkina,a   Petr P. Petrovskii,a   Alexander S. Konev,a   Dmitry S. Yufitb  and  Helen Stoeckli-Evansc  

* Corresponding authors

a Department of Chemistry, Saint Petersburg State University, Universitetskii pr. 26, St. Petersburg, Russia
E-mail: alexander.khlebnikov@pobox.spbu.ru
Fax: +7 812 4286939
Tel: +7 812 4284021

b Department of Chemistry, University of Durham, South Rd., Durham, UK
E-mail: d.s.yufit@durham.ac.uk
Fax: +44 191-334-2051
Tel: +44 191-334-2004

c Institute of Physics, University of Neuchâtel, rue Emile-Argand 11, Neuchâtel, Switzerland
E-mail: helen.stoeckli-evans@unine.ch
Fax: +41 32 7182511
Tel: +41 32 7182426

Abstract

An effective approach to azepino-fused heterocycles is described. trans-1-Aryl-7,11b-dihydro-1H-azirino[1,2-a]dibenzo[c,f]azepines were synthesised via a domino sequence: isomerization of gem-dichloroaziridine–intramolecular Friedel–Crafts acylation of the tethered benzene ring catalysed by SnCl4 and subsequent hydride induced intramolecular cyclization. Cycloaddition of dibenzazepinium ylides, generated by heating these aziridines, to activated C[double bond, length as m-dash]C, C[triple bond, length as m-dash]C dipolarophiles and fullerene C60, leads to derivatives of dibenzo[c,f]pyrrolo[1,2-a]azepine. The reaction proceeds with complete stereoselectivity via cycloaddition of only W-ylide, which due to the high barrier does not undergo E,Z-isomerization under the reaction conditions. It was found that 2,3,9,13b-tetrahydro-1H-dibenzo[c,f]pyrrolo[1,2-a]azepine systems can exist in conformations of two types depending on the substituents at the pyrrolidine carbons in β-position with respect to nitrogen. Details of cycloaddition reactions and the conformational behavior of cycloadducts were studied by DFT calculations at the B3LYP/6-31G(d) level.

Graphical abstract: An efficient approach to azirino and pyrrolo-fused dibenzazepines. Conformations of substituted dibenzo[c,f]pyrrolo[1,2-a]azepines

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Article information

DOI
https://doi.org/10.1039/C1OB05081H
Article type
Paper
Submitted
16 Jan 2011
Accepted
24 Feb 2011
First published
24 Feb 2011

Org. Biomol. Chem., 2011,9, 3886-3895

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An efficient approach to azirino and pyrrolo-fused dibenzazepines. Conformations of substituted dibenzo[c,f]pyrrolo[1,2-a]azepines

A. F. Khlebnikov, M. S. Novikov, M. V. Golovkina, P. P. Petrovskii, A. S. Konev, D. S. Yufit and H. Stoeckli-Evans, Org. Biomol. Chem., 2011, 9, 3886 DOI: 10.1039/C1OB05081H

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