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Synthesis 2021; 53(22): 4272-4278
DOI: 10.1055/a-1538-8429
special topic
Special Issue dedicated to Prof. Sarah Reisman, recipient of the 2019 Dr. Margaret Faul Women in Chemistry Award

A de novo Synthesis of Oxindoles from Cyclohexanone-Derived γ-Keto-Ester Acceptors Using a Desaturative Amination–Cyclization Approach

Henry P. Caldora‡
a   Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK
,
Sebastian Govaerts‡
a   Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK
,
Shashikant U. Dighe
a   Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK
,
Oliver J. Turner
b   Oncology R&D, Research & Early Development, AstraZeneca, Darwin building, 310, Cambridge Science Park, Milton Road, Cambridge CB4 0WG, UK
,
Daniele Leonori  ∗
a   Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK
› Author AffiliationsD.L. thanks the Engineering and Physical Sciences Research Council (EPSRC) for a Fellowship (EP/P004997/1) and the European Research Council for a research grant (No. 758427). H.C. thanks AstraZeneca for a Ph.D. Studentship.
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Dedicated to Prof Sarah Reisman in recognition on her award of the inaugural Margaret Faul Women in Chemistry Award.

Abstract

Here we report a desaturative approach for oxindole synthesis. This method uses simple ethyl 2-(2-oxocyclohexyl)acetates and primary amine building blocks as coupling partners. A dual photoredox–cobalt manifold is used to generate a secondary aniline that, upon heating, cyclizes with the pendent ester functionality. The process operates under mild conditions and was applied to the modification of several amino acids, the blockbuster drug mexiletine, as well as the formation of dihydroquinolinones.

Key words

photoredox - cobalt catalysis - dehydrogenative amination - late-stage modification - amino acids - oxindole

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1538-8429.
  • Supporting Information


Publication History

Received: 07 June 2021

Accepted after revision: 28 June 2021

Accepted Manuscript online:
28 June 2021

Article published online:
04 August 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

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