The [4 + 2] cross-benzannulation of conjugated enynes and diynes under cobalt-catalysis led to 1,2,3-trisubstituted benzene derivatives in good yields. The reaction proceeds smoothly in absolute regiospecific control when symmetrical diynes are applied. Moreover, the use of unsymmetrical diynes was investigated, resulting in the formation of the unprecedented regioisomers as major products, which is in contrast to the results obtained in palladium-catalyzed benzannulation reactions. Also, 4-bromophenyl-substituted starting materials could be applied successfully in the cobalt-catalyzed process, which can be problematic in the palladium-catalyzed counterpart.

Cobalt-Catalyzed Cross-Benzannulation of Conjugated Enynes and Diynes. -The [4 + 2] cross-benzannulation of conjugated enynes and diynes under cobalt--catalysis leads to 1,2,3-trisubstituted benzene derivatives in good yields. The reaction proceeds regioselectively when symmetrical diynes are applied. Reaction with unsymmetrical diynes results in the formation of the unprecedented regioisomers as major products, which is in contrast to the results obtained in palladium-catalyzed benzannulation reactions. Remarkably, 4-bromophenyl-substituted starting materials are successfully used in the cobalt-catalyzed process, which can be problematic in the palladium-catalyzed counterpart. -(ROESE, P.; GARCIA, C. C. M.; PUENNER, F.; HARMS, K.; HILT*, G.; J. Org. Chem. 80 (2015) 14, 7311-7316, http://dx.