Synfacts 2009(12): 1320-1320  
DOI: 10.1055/s-0029-1218231
Synthesis of Heterocycles
© Georg Thieme Verlag Stuttgart ˙ New York

Platinum-Catalyzed Synthesis of Pyrrolo[3,2-c]azepin-4-ones

Contributor(s): Victor Snieckus, Emilie David
M. Gruit, D. Michalik, A. Tillack, M. Beller*
Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Germany
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Publication History

Publication Date:
20 November 2009 (online)


Aiming to synthesize new pyrrolo[2,3-c]azepin-8-one derivatives 4 from the ­Sonogashira product 2 of the acetylenic pyrrole 1 under gold or platinum catalysis, Beller and co-workers unexpectedly obtained the isomeric pyrrolo[2,3-c]azepin-4-ones. Thus, instead of the expected endo-dig cyclization of 2 to give 4, the presumed initial acetylenic gold(III) or platinum(IV) complex undergoes C2 to C3 carbonyl migration prior to the alternative C2 endo-dig cyclization to yield the isomer 3. The reaction proceeds in the presence of AuCl3 or H2PtCl6˙6H2O, with H2PtCl6˙6H2O giving the best results. Alkynes with R = Ar gave moderate to good yields of products, whereas heteroaromatic-substituted alkynes led to poorer yields.