Theoretical study of 1,3-dipolar cycloadditions of nitrone and fulminic acid with substituted ethylenes
by Magnuson, E. C.; Pranata, J.
Molecular orbital calculations were performed to examine the electronic effects involved in the regioselectivity in the 1,3-dipolar cycloaddition reaction of nitrone and fulminic acid. The substituted ethylene dipolarophiles were selected to represent a range of electron-donating/withdrawing abilities: amino, methyl, carbaldehyde (both in the s-cis and the s-trans conformations), and nitrile. The reactions were all asynchronous, with early transition sites. The regioselectivity was correlated with the ability of the substituent to donate or withdraw electrons. With electron-donating substituents, the substituent was directed preferentially to the oxygen end of the dipole and this shifted toward the other regioisomer as the electron-withdrawing ability of the substitutent increased.
- Journal
- Journal of Computational Chemistry
- Volume
- 19
- Issue
- 16
- Year
- 1998
- Start Page
- 1795-1804
- URL
- https://dx.doi.org/10.1002/(sici)1096-987x(199812)19:16<1795::aid-jcc1>3.0.co;2-g
- ISBN/ISSN
- 1096-987X; 0192-8651
- DOI
- 10.1002/(sici)1096-987x(199812)19:16<1795::aid-jcc1>3.0.co;2-g