A series of γ-substituted α-methylidene-γ-butyrolactone
derivatives underwent regiospecific 1,3-dipolar cycloaddition with
N-methyl-C-phenylnitrilimine.
These reactions proceeded regiospecifically and with high
diastereoselectivity, generally favouring the anti
diastereomer as determined by n.m.r. spectroscopy and semiempirical molecular
orbital calculations. The assignment for one product was confirmed by X-ray
crystallography.
N-Methyl-C-phenylnitrilimine
underwent regiospecific cycloaddition with a range of C=S-containing
dipolarophiles. Substituted thioureas were generally unreactive as
dipolarophiles, while 5-thio-substituted
1,3,4-thiadiazole-2(3H)-thiones underwent ready reaction
to produce, rather than the expected cycloadducts, complex rearrangement
products. The structure of one of these unusual products has been confirmed by
X-ray crystallography. A series of disubstituted nitrilimines underwent
regiospecific cycloaddition with thiobenzophenone; the structures of the
products were confirmed by X-ray crystallography.