A computational study of anionic alkoxide–allene and amide–allene cyclizations

Florimond Cumine, Allan Young, Hans-Ulrich Reissig, Tell Tuttle, John A. Murphy

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Computational studies have been performed on potassium alkoxide-allenes, as well as potassium and lithium amido-allenes to probe the mechanism of their cyclizations to dihydrofurans and to 2,5-dihydropyrroles. A long-standing proposal envisaged electron transfer from dimsyl anions (formed by deprotonation of the solvent DMSO) but this pathway shows an exceptionally high kinetic barrier, while direct 5-endo-trig cyclization of the alkoxides and amides is much more easily achievable. The energy profiles for 4-exo-trig cyclizations onto the allenes are also explored, and the preferred formation of the observed five-membered products is rationalized.

LanguageEnglish
Pages6867-6871
Number of pages5
JournalEuropean Journal of Organic Chemistry
Volume2017
Issue number46
Early online date11 Oct 2017
DOIs
Publication statusPublished - 15 Dec 2017

Fingerprint

Cyclization
alkoxides
Amides
amides
potassium
Potassium
proposals
electron transfer
Deprotonation
lithium
anions
Dimethyl Sulfoxide
Lithium
Anions
probes
kinetics
products
profiles
Kinetics
Electrons

Keywords

  • alkoxyallenes
  • cyclization
  • density functional calculations
  • furans
  • heterocycles
  • pyrroles

Cite this

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abstract = "Computational studies have been performed on potassium alkoxide-allenes, as well as potassium and lithium amido-allenes to probe the mechanism of their cyclizations to dihydrofurans and to 2,5-dihydropyrroles. A long-standing proposal envisaged electron transfer from dimsyl anions (formed by deprotonation of the solvent DMSO) but this pathway shows an exceptionally high kinetic barrier, while direct 5-endo-trig cyclization of the alkoxides and amides is much more easily achievable. The energy profiles for 4-exo-trig cyclizations onto the allenes are also explored, and the preferred formation of the observed five-membered products is rationalized.",
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A computational study of anionic alkoxide–allene and amide–allene cyclizations. / Cumine, Florimond; Young, Allan; Reissig, Hans-Ulrich; Tuttle, Tell; Murphy, John A.

In: European Journal of Organic Chemistry, Vol. 2017, No. 46, 15.12.2017, p. 6867-6871.

Research output: Contribution to journalArticle

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