γ‐Valerolactone (GVL) was proposed as a renewable, nontoxic reaction medium with negligible vapor pressure for homogeneous Pd‐catalyzed aminocarbonylation reactions. Iodobenzene as a model substrate and its 4‐substituted derivatives were converted to the corresponding 2‐ketocarboxamides with high conversions and chemoselectivities in γ‐valerolactone. The effect of carbon monoxide pressure and reaction temperature on the conversion and selectivities were studied in the range 1–50 bar and 25–100 °C, respectively. The highest conversion and selectivity was achieved at 25 bar and 50 °C for iodobenzene in GVL for 24 h.

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