Alkylation of 2-and 3-alkoxycarbonyl-4-quinolinones. DFT study on the regioselectivity

作者：Shmidt Maria S; Manez Pau Arroyo; Stortz Carlos A; Perillo Isabel A; Vega Daniel; Blanco Maria M^*

来源：Journal of Molecular Structure, 2017, 1128: 142-150.

DOI：10.1016/j.molstruc.2016.08.057

• 4-Quinolones
• Alkylation
• Regioselectivity
• DFT
• B3LYP

The reaction of 2-alkoxycarbonyl-4-quinolinones (1) with a variety of alkylating reagents under different conditions, lead to the corresponding O-alkylated products. The behavior in basic medium of compounds 1 differs from the 3-alkoxycarbonyl-4-quinolinones (4) isomers suggesting that the position of the carboxylate group determines the regioselectivity of the reaction. OFT calculations allow us to conclude that for 3-alkoxycarbonyl-4-quinolinones, the N-alkylation would be thermodynamically and kinetically favored. But for 2-alkoxycarbonyl-4-quinolinones the side chain in the 2-position of the ring prevents the planar approximation to the contiguous heteroatom leading to a more favorable O-alkylation transition state. Crystal structure of an O-alkylated product is determined by single crystal X-ray diffractometry.

• 出版日期2017-1-15