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

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

doi:10.1002/ejoc.201701381

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

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

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

22 Downloads (Pure)

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.

Original language	English
Pages (from-to)	6867-6871
Number of pages	5
Journal	European Journal of Organic Chemistry
Volume	2017
Issue number	46
Early online date	11 Oct 2017
DOIs	https://doi.org/10.1002/ejoc.201701381
Publication status	Published - 15 Dec 2017

Keywords

alkoxyallenes
cyclization
density functional calculations
furans
heterocycles
pyrroles

Access to Document

10.1002/ejoc.201701381

Cumine-etal-EJOC-2017-A-computational-study-of-anionic-alkoxide-allene-and-amide–allene-cyclizationsAccepted author manuscript, 1.35 MB

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title = "A computational study of anionic alkoxide–allene and amide–allene cyclizations",

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.",

keywords = "alkoxyallenes, cyclization, density functional calculations, furans, heterocycles, pyrroles",

author = "Florimond Cumine and Allan Young and Hans-Ulrich Reissig and Tell Tuttle and Murphy, {John A.}",

note = "This is the pre-peer reviewed version of the following article: Cumine, F., Young, A., Reissig, H-U., Tuttle, T., & Murphy, J. A. (2017). A computational study of anionic alkoxide–allene and amide–allene cyclizations. European Journal of Organic Chemistry, 2017(46), 6867-6871., which has been published in final form at https://doi.org/10.1002/ejoc.201701381. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.",

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AU - Reissig, Hans-Ulrich

AU - Tuttle, Tell

AU - Murphy, John A.

N1 - This is the pre-peer reviewed version of the following article: Cumine, F., Young, A., Reissig, H-U., Tuttle, T., & Murphy, J. A. (2017). A computational study of anionic alkoxide–allene and amide–allene cyclizations. European Journal of Organic Chemistry, 2017(46), 6867-6871., which has been published in final form at https://doi.org/10.1002/ejoc.201701381. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

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N2 - 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.

AB - 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.

KW - alkoxyallenes

KW - cyclization

KW - density functional calculations

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KW - heterocycles

KW - pyrroles

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