Photodissociation of the Product from a Transition-Metal Center Allows the Catalytic Cycle to Proceed: The Rhodium(I)-Catalyzed [2+2+1] Carbonylative Cycloaddition of Diynes.

We describe the effective rhodium(I)-catalyzed [2+2+1] carbonylative cycloaddition of diynes, yielding cyclopentadienes (CPDs), under photoirradiation. The catalysis involves the promotion of the photodissociation of the product CPD, with the simultaneous production of an essential vacant coordination site on the rhodium for an unreacted substrate. The combined use of cationic [Rh(cod)2]BF4 as a catalyst and photoirradiation was also found to give various CPDs in high yields (≤96%).