Synthesis of 2-Acylindoles via Ag- and Cu-Catalyzed anti-Michael Hydroamination of β-(2-Aminophenyl)-α,β-ynones: Experimental Results and DFT Calculations

The Journal of Organic Chemistry
Navnath D RodeFabio Marinelli

Abstract

β-(2-Aminophenyl)-α,β-ynones afforded 3-unsubstituted 2-acylindoles in good yields in the presence of 20 mol % AgOTf under (microwave) MW heating. The use CuOTf as a catalyst resulted in a similar reaction outcome, generally with a lower efficiency. This transformation represents the first example of 5- endo-dig cyclization of 2-alkynylanilines bearing an acyl group linked to the triple bond. By contrast with the previously reported gold-catalyzed reaction of β-(2-aminophenyl)-α,β-ynones, which resulted in the formation of dibenzo[1,5]diazocines through a sequential process triggered by an intermolecular hydroamination, a selective intramolecular anti-Michael hydroamination was observed in the present study by silver/copper catalysis. Density functional theory calculations on the Ag-catalyzed reaction revealed that the catalyst induces an electrostatic arrangement in the TS coherent with the experimentally observed cyclization.

References

Jun 10, 2004·Chemical Reviews·Francisco AlonsoMiguel Yus
Jul 14, 2005·Chemical Reviews·Sandro Cacchi, Giancarlo Fabrizi
Aug 12, 2005·Chemical Reviews·Jacopo TomasiRoberto Cammi
Dec 17, 2008·Chemistry : a European Journal·David TejedorFernando García-Tellado
Apr 13, 2010·Chemical Reviews·Anna J Kochanowska-Karamyan, Mark T Hamann
Nov 30, 2010·European Journal of Medicinal Chemistry·Martin ArthuisJean-Claude Florent
May 6, 2011·The Journal of Organic Chemistry·Kazumi OkuroHoward Alper
Jul 23, 2011·Organic & Biomolecular Chemistry·Rubén Vicente
Apr 20, 2012·Chemical Communications : Chem Comm·Bing ZhouYuanchao Li
Oct 24, 2012·Bioorganic & Medicinal Chemistry·Masafumi KomiyaYoshiaki Isobe
Mar 2, 2013·Chemical Communications : Chem Comm·Changduo PanChengjian Zhu
Mar 8, 2013·Natural Product Reports·Minoru IshikuraSatoshi Hibino
Jun 6, 2014·Chemical Communications : Chem Comm·Yogesh Goriya, Chepuri V Ramana
Jun 28, 2014·Journal of the American Chemical Society·Roohollah Kazem ShiroodiVladimir Gevorgyan
Dec 3, 2014·European Journal of Medicinal Chemistry·Ming-Zhi ZhangGuang-Fu Yang
Jul 30, 2015·Chemical Society Reviews·Guichun Fang, Xihe Bi
Sep 12, 2015·The Journal of Organic Chemistry·Michael J StephensonMark Searcey
Nov 10, 2015·Chemistry : a European Journal·Dattatraya Hanumant Dethe, Raghavender Boda

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Citations

Sep 28, 2018·Organic & Biomolecular Chemistry·Miao HuHuanfeng Jiang
Aug 1, 2020·Beilstein Journal of Organic Chemistry·Dalel El-MarroukiPhilippe C Gros
Mar 26, 2019·Chemistry, an Asian Journal·Aimee K ClarkeWilliam P Unsworth
May 7, 2021·The Journal of Organic Chemistry·Alexander A GolovanovStanislav A Grabovskiy
May 28, 2021·Organic & Biomolecular Chemistry·Vincenzo MarsicanoAntonia Iazzetti
Apr 11, 2020·Organic Letters·Amol Milind GarkhedkarJeh-Jeng Wang

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