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Cationic Rh(I)/modified-BINAP-catalyzed reactions of carbonyl compounds with 1,6-diynes leading to dienones and ortho-functionalized aryl ketones.

We have determined that a cationic rhodium(I)/H8-BINAP complex catalyzes a [2 + 2 + 2] cycloaddition of both activated and unactivated carbonyl compounds with 1,6-diynes leading to dienones in high yields. On the other hand, unactivated aryl ketones react with 1,6-diynes in the presence of a cationic rhodium(I)/Segphos complex to give ortho-functionalized aryl ketones in high yields.