Photochemical Generation of Allenylidenes from Cyclopropanated Phenanthrenes: An Experimental and Computational Study

To address the scarcity of generally applicable photochemical routes to allenylidenes in solution, phenanthrene-based sources have been investigated. Specifically, the syntheses of 1-vinylidene-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene, 1-(2-phenylvinylidene)-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene, and 1-(2-methylvinylidene)-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene, photochemical precursors to propadienylidene, 3-phenylpropadienylidene, and 3-methylpropadienylidene have been carried out. Photolysis of these new precursors in olefin traps and benzene afforded the expected cyclopropane adducts of the corresponding allenylidenes. Quantum chemical calculations show that the ground state of all three carbenes is a singlet with a singlet-triplet gap of ∼29, 30, and 33 kcal/mol for propadienylidene, 3-phenylpropadienylidene, and 3-methylpropadienylidene, respectively.