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.
| Language | English |
|---|---|
| Pages | 6867-6871 |
| Number of pages | 5 |
| Journal | European Journal of Organic Chemistry |
| Volume | 2017 |
| Issue number | 46 |
| Early online date | 11 Oct 2017 |
| DOIs | |
| Publication status | Published - 15 Dec 2017 |
Fingerprint
Keywords
- alkoxyallenes
- cyclization
- density functional calculations
- furans
- heterocycles
- pyrroles
Cite this
}
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 journal › Article
TY - JOUR
T1 - A computational study of anionic alkoxide–allene and amide–allene cyclizations
AU - Cumine, Florimond
AU - Young, Allan
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.
PY - 2017/12/15
Y1 - 2017/12/15
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
KW - furans
KW - heterocycles
KW - pyrroles
UR - http://www.scopus.com/inward/record.url?scp=85038106483&partnerID=8YFLogxK
U2 - 10.1002/ejoc.201701381
DO - 10.1002/ejoc.201701381
M3 - Article
VL - 2017
SP - 6867
EP - 6871
JO - European Journal of Organic Chemistry
T2 - European Journal of Organic Chemistry
JF - European Journal of Organic Chemistry
SN - 1434-193X
IS - 46
ER -