[reaction: see text] Novel synthetic methods of both ortho-alkenylated aromatic ketones and isoquinoline derivatives have been developed through the Rh(I)-catalyzed direct ortho-alkenylation of common aromatic ketimines with alkynes. Furthermore, a highly efficient one-pot synthesis of isoquinoline derivatives was achieved by simply mixing aromatic ketone, benzylamine, and alkyne under a Rh(I) catalyst.

Herein we describe the chelation‐assisted CH and CC bond activation of carbonyl compounds by RhI catalysts. Hydroacylation of olefins was accomplished by utilizing 2‐amino‐3‐picoline as a chelation auxiliary. The same strategy was employed for the CC bond activation of unstrained ketones. Allylamine 24 was devised as a synthon of formaldehyde. Hydroiminoacylation of alkynes with allylamine 24 was applied to the alkyne cleavage by the aid of cyclohexylamine.

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An allylic alcohol, utilized as a precursor for an aliphatic aldehyde, reacted with olefins to afford aliphatic ketones in the presence of RhCl(PPh(3))(3), 2-amino-4-picoline, aniline, and benzoic acid through a tandem reaction of an isomerization and a chelation-assisted hydroacylation.