Combination of transition metal catalysis with organocatalysis in ways of synergetic catalysis, cooperative catalysis, or/and sequential catalysis has been emerged as a powerful strategy to promote organic transformations that cannot be achieved by each individual independently. Herein, a new protocol for the synthesis of primary amides from olefins, CO and NH3 through one-pot tandem methoxycarbonylation-aminolys was presented over a bi-functional ligand (Li) based rhodium catalyst with functions of co-catalysis. Li is composed of the phosphino-fragment and the amino-/imino-tautomeric moiety. Then Ll-based Rh-catalytic system demonstrated a combination of Rh-P transition metal catalysis and the tautomeric catalysis. In this tandem methoxycarbonylation-aminolysis, NH3 also served as a ligand to work together with the phosphino-fragment to synergetically modify the performance of Rh-catalyst responsible for the first-step methoxycarbonylation of olefin to generate the esters, and the Rh-tailed tautomeric catalyst was in charge of the subsequent aminolysis to generate the targeted primary amides. (C) 2018 Elsevier Inc. All rights reserved.