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Scientific article
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English

Coumarin synthesis on π-acidic surfaces

Published inSupramolecular chemistry, vol. 27, no. 5-6, p. 303-309
Publication date2015
Abstract

Catalysis with anion–π interactions is emerging as an important topic in supramolecular chemistry. Among the reactions explored so far on π-acidic surfaces, coumarin synthesis stands out as a cascade process with several coupled anionic transition states. Increasing π-acidity has been shown in a different context to increase transition-state stabilisation and thus catalytic activity. In this report, we explore the possible use of macrocycles to accelerate coumarin synthesis between two π-acidic surfaces. To our disappointment, we found that compared to monomeric π-acids, coumarin synthesis within divalent macrocycles is clearly slower. Hindered access to an overly confined active site within the macrocycles could possibly account for this loss in activity, but several other explanations are certainly possible. However, operational coumarin synthesis on monomeric π-acidic surfaces is shown to tolerate structural modifications. Best results are obtained with structures that aim for proximity without obstructing transition-state stabilisation on the π-acidic surface.

Keywords
  • Anion–π interactions
  • Catalysis
  • Anionic transition states
  • Enolates
  • Naphthalenediimides
  • Macrocycles
Citation (ISO format)
MIROS, François et al. Coumarin synthesis on π-acidic surfaces. In: Supramolecular chemistry, 2015, vol. 27, n° 5-6, p. 303–309. doi: 10.1080/10610278.2014.959013
Main files (2)
Article (Published version)
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Article (Accepted version)
Identifiers
ISSN of the journal1026-7816
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