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The stereochemical outcomes observe
d in the thermal an
d microwave-assiste
d [3 + 2] cycloa
dditionbetween stabilize
d azomethine yli
des an
d nitrostyrenes have been analyze
d using experimental an
dcomputational approaches. It has been observe
d that, in the absence of solvent, three stereoisomers areforme
d, both un
der classical heating con
ditions an
d un
der microwave irra
diation. This result contrastswith that observe
d in solution un
der classical thermal con
ditions. The 4-nitropyrroli
dines obtaine
d inthis way can be aromatize
d un
der further microwave irra
diation to yiel
d mixtures of pyrroles an
d4-nitropyrroles. It is foun
d that groun
d state cycloa
dditions between imines an
d nitrostyrenes take placeby three-step mechanisms. The first step involves enolization of the starting imine, an
d this is followe
dby a pseu
dopericyclic 10-electron [1.4]-hy
drogen shift. Finally, the cycloa
ddition takes place by a relativelyasynchronous aromatic six-electron
supra-supra thermal mechanism.