Efficient and Selective Synthesis of Crownopaddlanes Possessing Two Cyclobutane Rings and Exclusive Complexation of Lithium.

A new type of crown compounds (crownopaddlanes) bearing two cyclobutane rings were efficiently and selectively prepared by means of intramolecular [2 + 2] photocycloaddition of appropriate styrene derivatives, which was successfully carried out in cyclohexane under irradiation through a Pyrex filter. Crownopaddlanes 4a, 5, and 6 exclusively and quantitatively extracted Li(+) on the solid-liquid extraction. Upon the competitive extraction, 4a showed the highest selectivity toward Li(+) over Na(+) and K(+) (Li(+)/Na(+) = 610, Li(+)/K(+) = 976). The structural factors working in the complexation of the crownopaddlane were examined by X-ray crystallographic analysis.