RESUMO
The palladium-catalyzed annulation of 9-bromo- and 9-chlorophenanthrenes with alkynes gave 4,5-disubstituted acephenanthrylenes in yields of 58-95% (9 examples). Asymmetric alkynes, such as 1-phenyl-1-propyne, 1-phenyl-1-hexyne, and 1-cyclopropyl-2-phenylethyne, regioselectively form (cyclo)alkyl-substituted products, following the regular rule that governs the carbopalladation of alkynes. This synthetic protocol can also be utilized in annulations with several π-extended bromoarenes, such as 7-bromo[5]helicene, 5-bromo[4]helicene, 9-bromoanthracene, 3-bromoperylene, and 3-bromofluoranthene, to give the corresponding annulated products in moderate to good yields (51-86%; 6 examples). Similarly, bromocorannulene produced highly curved 1,2-disubstituted cyclopentacorannulenes. Reactions of 6,12-dibromochrysene and 4,7-dibromo[4]helicene with di(4-tolyl)ethyne provided the twofold annulated products in moderate yields. 4,5-Diphenylacephenanthrylene and 6,7-diphenylbenzo[a]acephenanthrylene thus generated were converted into phenanthro[9,10-e]acephenanthrylene and benzo[a]phenanthro[9,10-e]acephenanthrylene, respectively, by oxidative cyclodehydrogenation. The structures of 4,5-diphenylacephenanthrylene, 4,5-diphenyldibenzo[a,l]acephenanthrylene, 1,2-diarylcyclopentacorannulenes, and benzo[a]phenanthro[9,10-e]acephenanthrylene were verified by X-ray crystallography. The photophysical and electrochemical properties of the selected annulated products were investigated.
RESUMO
Highly curved buckybowls 3, 4, and 5 were synthesized from planar precursors, fluoranthenes 8, benzo[k]fluoranthenes 10 and naphtho[1,2-k]-cyclopenta[cd]fluoranthenes 12, respectively, using straightforward palladium-catalyzed cyclization reactions. These fluoranthene-based starting materials were easily prepared from 1,8-bis(arylethynyl)naphthalenes 6. Both buckybowls 3 and 4 are fragments of C60 , whereas 5 is a unique subunit of C70 . The curved structures were identified by X-ray crystallography, and they are deep bowls. The maximum π-orbital axis vector (POAV) pyramidalization angle in both 3 and 4 is 12.8°. Such a high curvature is very rarely obtained. Buckybowls 5 are less curved than the others because they have a lower density of five-membered rings, analogous to the tube portion of C70 . Cyclopentaannulation increases the bowl depths of 3 and 4, but not the maximum POAV pyramidalization angle. Among the eight buckybowls studied herein, five form polar crystals. The bowl-to-bowl inversion dynamics of these buckybowls can be classified into two types; one has a planar transition structure, whereas the other has an S-shaped transition structure. A larger longitudinal length of these buckybowls corresponds to a stronger preference for the latter. The photophysical properties of these buckybowls were examined and compared with those of C60 and C70 . Buckybowls 5 have absorption bands at wavelengths greater than 450â nm, which are similar to those of C70 . The chiral resolution of the mono-substituted buckybowl 4 ac was also studied by using HPLC with a chiral column.