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Cycloadditions of Aryl‐Substituted 1,2,4‐Triazines with 2‐Cyclopropylidene‐1,3‐dimethylimidazolidine – Zwitterions as Discrete Intermediates
Author(s) -
Ernd Michael,
Heuschmann Manfred,
Zipse Hendrik
Publication year - 2005
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200590120
Subject(s) - chemistry , steric effects , regioselectivity , nucleophile , aryl , medicinal chemistry , computational chemistry , triazine , stereochemistry , organic chemistry , catalysis , alkyl
Cycloadditions of 2‐cyclopropylidene‐1,3‐dimethylimidazolidine ( 1 ), a strong, electron‐rich C‐nucleophile, with a variety of aryl‐substituted 1,2,4‐triazines occur at temperatures between −100 and +100°, depending on the substitution pattern. At low temperatures, zwitterions, formed by nucleophilic attack of 1 on the triazines, could be detected spectroscopically and, in some cases, isolated. Two types of zwitterions were found: 1 ) those where the new bond was linked to C(5) of the triazine and which were formed in a reversible dead‐end equilibrium, and 2 ) those where the new bond was linked either to C(3) or C(6). The latter exhibited the same regiochemistry as the final cycloadducts, and might be intermediates of a two‐step Diels–Alder reaction. Energies and structural characteristics for stationary points in the reaction of monosubstituted triazines with 1 in the gas phase and in CH 2 Cl 2 solution were calculated at the Becke3LYP/6‐311+G(d,p)//Becke3LYP/6‐31G(d) level of theory. Different reaction mechanisms are discussed on the basis of steric, electronic, and solvent effects.