Cuthbertson, J;
Wilden, JD;
(2015)
Z-selective, anti-Markovnikov addition of alkoxides to terminal alkynes: an electron transfer pathway?
Tetrahedron
, 71
(25)
pp. 4385-4392.
10.1016/j.tet.2015.04.038.
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Abstract
Potassium alkoxides undergo anti-Markovnikov addition to aryl-substituted alkynes with Z selectivity in DMF as the solvent. The yields and efficiency of the reaction was also found to be enhanced by the addition of a secondary amine ligand such as N,N′-dimethylethylenediamine. Mechanistic investigations suggest that the products, reaction rates and selectivity can be explained via a single electron transfer from the alkoxide to the alkyne. This leads to a radical anion intermediate, which then rapidly combines with the alkoxide to yield a vinyl anion whose lifetime governs the E:Z selectivity observed in the products.
| Type: | Article |
|---|---|
| Title: | Z-selective, anti-Markovnikov addition of alkoxides to terminal alkynes: an electron transfer pathway? |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1016/j.tet.2015.04.038 |
| Publisher version: | http://dx.doi.org/10.1016/j.tet.2015.04.038 |
| Language: | English |
| Additional information: | © 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/) |
| Keywords: | Radicals, Alkynes, Enol ethers, Electron transfer, Alkoxides |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/1471635 |
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