Alkyl-, vinyl- and aryllithium reagents and an ester enolate added efficiently and highly regioselectively ortho to the aromatic substituent of tricarbonyl(4,5-dihydro-4,4-dimethyl-2-phenyloxazole)chromium(0) (1) and tricarbonyl(benzylidene-cyclohexylamine)chromium(0) (2) complexes. The tertiary carbanion 2-lithio-2-methylpropionitrile gave a 3:1 para/meta selectivity. Complex 1 was obtained via arene exchange in tricarbonyl(naphthalene)chromium(0).