Successive regio-and chemoselective metalations of chloropyrazines using TMPMgCl· LiCl and TMPZnCl· LiCl furnish, after trapping with electrophiles, highly functionalized pyrazines in high yields. Application to a synthesis of coelenterazine, a bioluminescent natural product in jellyfish Aequorea victoria, in nine steps (9% overall yield) is reported.