Synthesis of bicyclic dioxetanes bearing a 2-hydroxy-1,1′-binaphthyl-5-yl moiety active toward intramolecular charge-transfer-induced chemiluminescent decomposition

Five pairs of diastereoisomeric dioxetanes, cis- and trans-2a–2e, were synthesized. These dioxetanes underwent intramolecular charge-transfer-induced decomposition with accompanying emission of orange light in TBAF in DMSO (system A) as a complete homogeneous system and in [K⊂(18C6)]+t-BuO− in PhH–THF (system B) as a sterically anisotropic environment. Maximum wavelength (λmaxCTICL) of chemiluminescence did not vary practically with the triggering system. The λmaxCTICL was little affected also by substituents on the upper-Nap of dioxetanes 2, nor by the difference in their stereochemistry, namely, cis- or trans-isomer. On the other hand, chemiluminescent efficiency was found to split up depending on stereochemistry of 2. Dioxetane 2b bearing a methoxycarbonyl group on the upper-Nap gave significantly weak light, while its free carboxylic acid analog 2c afforded light effectively.