کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5217194 | 1383287 | 2014 | 7 صفحه PDF | دانلود رایگان |
Computational calculations of the hetero-Diels-Alder (HDA) reactions of benzaldehyde with 2,3-dimethyl-1,3-butadiene (DMB) catalyzed by BF3, EtAlCl2 or TiCl4 at the density functional theory (DFT) (B3LYP/6-31G(d,p)) level reveal that the reactions involve activation energy barriers of 14.59, 14.34, and 17.44 kcal molâ1, respectively. In the first two cases, reaction occurs through a concerted mechanism, whereas in the presence of TiCl4, stepwise mechanism involving zwitterionic intermediate is followed. The reaction with isoprene proceeds with complete regioselectivity leading to the expected regioisomer having O/Me in 1:4 positions. The computational results have been verified experimentally when aromatic aldehydes react with 1,3-dienes in the presence of a catalyst to give 3,6-dihydro-2H-pyran derivatives in high yields.
Journal: Tetrahedron - Volume 70, Issue 3, 21 January 2014, Pages 735-741