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Theoretical study of 1,3‐dipolar cycloadditions of nitrone and fulminic acid with substituted ethylenes
Author(s) -
Magnuson Eric C.,
Pranata Julianto
Publication year - 1998
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(199812)19:16<1795::aid-jcc1>3.0.co;2-g
Subject(s) - regioselectivity , substituent , chemistry , nitrone , nitrile , cycloaddition , polar effect , 1,3 dipolar cycloaddition , computational chemistry , medicinal chemistry , stereochemistry , organic chemistry , catalysis
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. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1795–1804, 1998