Bicyclo[6.3.0]undeca-1(11),2,4,6,8-pentaen-10-ylidene: An Aromatic Carbene with Ambiphilic Properties

The title carbene (4) was generated as a highly reactive species in solution by photoirradiation of 10-diazobicyclo[6.3.0]undecapentaene (5) using a high-pressure mercury lamp. Carbene 4 reacts with benzene to afford two isomeric adducts, 10-phenylbicyclo[6.3.0]undecapentaene (10) and tricyclo[9.3.0^3, 10 .0]heptadeca-1,3(10),4,6,8,12,14,16-octaene (11). The reactivity toward benzene is a characteristic of an electrophilic aromatic carbene analogous to cyclopentadienylidene 1. In contrast, the reaction of 4 with methanol produces 7-methoxybicyclo[6.3.0]undeca-1,3,5,8,10-pentaene (15). When [D₁ ]methanol was employed as a reactant, the 10-deuterated analogue was formed. The results clearly indicate the formation of bicyclo[6.3.0]undecapentaenyl cation (7) as a novel 10 π-electronic compound by protonation of 4. Theoretical calculations indicate that the 2- and 7-positions of the cation have the largest positive charge in the cation. Moreover, the carbene was generated in the presence of tert-butyl hydroperoxide in aqueous tetrahydrofuran to afford azulene through oxidation of 7, followed by decarbonylation. The nucleophilic property of carbene 3 is similar to that of cycloheptatrienylidene 2. Thus, 4 can be regarded as a novel ambiphilic aromatic carbene.