Highly distorted and rigid cone conformers of calix[4]arene have been
synthesized by low-valent titanium promoted intra-molecular coupling o
f aldehydes 1a-d. The reaction outcome strongly depends on the substit
uents present at the upper rim and reaction time. In all cases examine
d intramolecular coupled compounds, having a bridge only two atoms lon
g, were obtained in about 30% yield.