Computational Characterization of the Origin of Selectivity in Cycloaddition Reactions Catalyzed by Phosphoric Acid Derivatives

Chunhui Liu, Maria Besora, Feliu Maseras

Research output: Contribution to journalArticleResearchpeer-review

16 Citations (Scopus)

Abstract

© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. The mechanism of the organocatalyzed [4+2] cycloaddition of ο-hydroxybenzaldimines to 2,3-dihydro-2 H-furan (DHF) to form furanobenzopyrans has been investigated by using computational methods. Experiments have shown that this reaction produces different products (trans-fused or cis-fused) if different phosphoric acid derivatives are applied. Our study shows the reaction proceeds through a mechanism in which the imine re-arranges into an amine, which subsequently reacts with DHF with mediation from the catalyst. The rate-limiting step in this process is the formation of two new bonds, which is also the key step in determining the reaction selectivity. The selectivity is controlled by a balance of noncovalent interactions between the catalyst and the substrates. The discriminating factor between the two catalysts is the presence of a triflyl substituent on one of catalysts, which constraints the relative orientations of the substrates.
Original languageEnglish
Pages (from-to)411-416
JournalChemistry - An Asian Journal
Volume11
Issue number3
DOIs
Publication statusPublished - 4 Feb 2016

Keywords

  • computational chemistry
  • cycloaddition
  • density functional theory
  • organocatalysis
  • phosphoric acid esters

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