N-Alkoxyacrylamides are coupled with N-phenoxyacetamides by RhIII catalysis through C–H functionalization and amido group transfer under external oxidant-free conditions, which affords acyclic alkene carboamination products in an atom-economical way. Mechanistic insight into this transformation indicates the amide group in N-alkoxyacrylamide plays a critical role in this C–C/C–N bond formation reaction. This methodology provides a highly efficient way to construct o-tyrosine derivatives under mild conditions.