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Scientific article
English

Copper(ii) chloride mediated (aza)oxindole synthesis by oxidative coupling of Csp2–H and Csp3–H centers: substrate scope and DFT study

Published inOrganic & biomolecular chemistry, vol. 11, no. 39, p. 6734-6743
Publication date2013
Abstract

A CuCl2 mediated direct intramolecular oxidative coupling of Csp2–H and Csp3–H centers gives access to 3,3-disubstituted oxindoles containing aromatic, heteroaromatic and alkyl substituents as well as a heteroatom at the quaternary center in good to excellent yields. The reaction is carried out in the presence of NaOtBu and CuCl2 in DMF at 110 °C. The key step of this reaction is the formation of an amidyl radical by one electron oxidation of amide enolate followed by an intramolecular radical cyclization reaction (homolytic aromatic substitution reaction). A detailed DFT study shows that the cyclization of the amidyl radical is the rate-limiting step in the oxindole synthesis, whereas the second single electron transfer (SET) becomes the rate-determining step in the aza-oxindole formation. Computational data are in agreement with the experimentally observed relative reactivity and regioselectivity.

Citation (ISO format)
DEY, Chandan, LARIONOV, Evgeny, KUNDIG, Ernst Peter. Copper(ii) chloride mediated (aza)oxindole synthesis by oxidative coupling of C<sub>sp2</sub>–H and C<sub>sp3</sub>–H centers: substrate scope and DFT study. In: Organic & biomolecular chemistry, 2013, vol. 11, n° 39, p. 6734–6743. doi: 10.1039/c3ob41254g
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ISSN of the journal1477-0520
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