The activation of C-H and C-C bonds by transition metal complexes has received considerable attention in organometallic chemistry.¹ In particular, chelation assisted hydroacylation of alkenes or alkynes with aldehydes is important because the corresponding ketone is atom-economically produced.² Herein, we developed chelation-assisted Rh(I)-catalyzed dialkyl ketone synthesis through C–H and C–C bond activations of allylic alcohol under microwave irradiation.³ In this process, the aldimine is formed through olefin isomerization of allyl alcohol under Rh(I) catalyst and condensation with 2-amino-3-picoline. And the resulting aldimine compound reacts with the alkene via continuous C–H and C–C bond activations under chelation assisted Rh(I) catalyst to produce the dialkyl ketone. The addition of piperidine accelerates the reaction rate by promoting aldimine formation under microwave conditions.