Herein we describe the chelation-assisted C-H and C-C bond activation of carbonyl compounds by Rh1 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.