Selective functionalization at the α-methyl group of 1-substituted pyridin-2(1H)- and 4(1H)-ones (2- and 4-pyridones) can be achieved by appropriate choice of base. n-Butyllithium was found to effect clean 6(2)-methyl deprotonation of 1-benzyl-2- and -4-pyridone derivatives, while potassium hexamethyldisilazide (KHMDS) was the preferred reagent for methyl deprotonation of the corresponding 1-methyl-2- and -4-pyridones. Deprotonation proceeds smoothly at –78 °C, and the resulting anions react readily with a wide range of electrophiles (aldehydes, ketones, alkylating reagents, and an azo compound) under precise temperature control to form usefully functionalized 2- and 4-pyridones and quinolizinones.
Funding
We thank AstraZeneca and Loughborough University for financial support, and the Engineering and Physical Sciences Research Council (EPSRC) UK National Mass Spectrometry Facility at Swansea for mass spectra.
History
School
Science
Department
Chemistry
Published in
European Journal of Organic Chemistry
Citation
FERNANDEZ D.-R., B. ... et al, 2016. Pyridone functionalization: regioselective deprotonation of 6-methylpyridin-2(1H)- and -4(1H)-one derivatives. European Journal of Organic Chemistry, 2016(31), pp. 5238–5242.
This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/
Acceptance date
2016-09-16
Publication date
2016
Notes
This is the peer reviewed version of the following article: FERNANDEZ D.-R., B. ... et al, 2016. Pyridone functionalization: regioselective deprotonation of 6-methylpyridin-2(1H)- and -4(1H)-one derivatives. European Journal of Organic Chemistry, 2016(31), pp. 5238–5242., which has been published in final form at http://dx.doi.org/10.1002/ejoc.201601156. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.