Computational studies on the electrocyclizations of 1-amino-1,3,5-hexatrienes

Guner, VİLDAN; Houk, KN; Davies, IW

doi:10.1021/jo048540s

Computational studies on the electrocyclizations of 1-amino-1,3,5-hexatrienes

Guner V., Houk K., Davies I.

JOURNAL OF ORGANIC CHEMISTRY, vol.69, no.23, pp.8024-8028, 2004 (SCI-Expanded, Scopus)

Publication Type: Article / Article
Volume: 69 Issue: 23
Publication Date: 2004
Doi Number: 10.1021/jo048540s
Journal Name: JOURNAL OF ORGANIC CHEMISTRY
Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
Page Numbers: pp.8024-8028
Hacettepe University Affiliated: Yes

Abstract

Electrocyclizations of 1,3,5-hexatrienes containing up to four electron-donating and/or electron withdrawing substituents have been studied computationally using the hybrid density functional, B3LYP. Electron donating substituents at positions C-1 and C-5 decrease activation barriers by 0.3 to 2.3 kcal/mol. Introducing of an electron-withdrawing group, CO2Me, at C-4 further decreases the activation energy by 7 kcal/mol. Electron-withdrawing groups (NO2, SO2Ph and C=N+Me-2) at C-2 have a profound effect of 17-25 kcal/mol on the activation energy.