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Synthesis 2017; 49(23): 5203-5210
DOI: 10.1055/s-0036-1590880
DOI: 10.1055/s-0036-1590880
paper
Synthesis of 3,3-Disubstituted 2-Oxindoles by Deacylative Alkylation of 3-Acetyl-2-oxindoles
We gratefully acknowledge financial support from the Spanish Ministerio de Ciencia e Innovación (MICINN) (projects CTQ2010-20387 and Consolider Ingenio 2010, CSD2007-00006), the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects CTQ2016-76782-P and CTQ2016-81797-REDC), the Generalitat Valenciana (PROMETEO2009/039 and PROMETEOII/ 2014/017) and the University of Alicante. A.O.-M. thanks MINECO for a predoctoral fellowship.Further Information
Publication History
Received: 09 June 2017
Accepted after revision: 22 July 2017
Publication Date:
22 August 2017 (online)
Abstract
An innovative and efficient monoalkylation and nonsymmetrical 3,3-dialkylation of oxindoles has been achieved. First, the monoalkylation of 3-acetyl-2-oxindoles can be performed in good yields under mild reaction conditions using alkyl halides and benzyltrimethylammonium hydroxide (Triton B) as base at room temperature. This methodology is applied to construct the synthetically challenging compound 1,3-dimethyl-2-oxindole. Subsequent deacylative alkylation (DaA) of the alkylated 3-acetyl-2-oxindoles with alkyl halides takes place efficiently using LiOEt or by conjugate addition with electron-deficient alkenes in the presence of Triton B at room temperature under argon, affording the corresponding unsymmetrically 3,3-disubstituted 2-oxindoles. This simple methodology has been applied to the synthesis of precursors of horsfiline, esermethole, physostigmine, and phenserine alkaloids.
Supporting Information
- Copies of 1H and 13C NMR spectra of new products.Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590880.
- Supporting Information
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