Bioinspired palladium‐catalyzed intramolecular cyclization of amino acid derivatives containing a vinyl iodide moiety by C−H activation enabled rapid access to a wide range of functionalized proline derivatives with an exocyclic olefin. To demonstrate the practicality of this methodology, the functionalized prolines were used as intermediates for the synthesis of several natural products: lucentamycin A, oxotomaymycin, oxoprothracarcin, and barmumycin. Bioinspired palladium(II)‐catalyzed intramolecular cyclization of amino acid derivatives containing a vinyl iodide moiety by C−H activation enabled rapid access to a wide range of functionalized proline derivatives with an exocyclic double bond. Such functionalized prolines were used as intermediates for the total synthesis of several natural products: lucentamycin A, barmumycin, oxotomaymycin, and oxoprothracarcin.