A concise seven-step asymmetric synthesis of MSD's potent hNK 1 antagonist containing a pyrrolizidinone core bearing two fluorine-substituted aryl groups was developed. The pyrrolizidinone unit was constructed by reductive recyclization of a properly functionalized cyclic nitronate, which was assembled by stereoselective [4 + 2]-cycloaddition of a nitroalkene with a vinyl ether bearing a Whitesell's chiral auxiliary group. The configuration of the hNK 1 antagonist, which was previously suggested based on bioactivity data, was confirmed by X-ray analysis. The crystal structure features multiple weak interactions involving fluorine atoms that are also found in a complex with the hNK 1 receptor simulated by molecular docking.