C3-selective direct coupling reactions of unsaturated 5-membered heterocycles such as 2,5-dihydrofuran, N-tosyl-2,5-dihydropyrrole, and 3-sulfolene with methyl methacrylate or methacryl amide are catalyzed by [Ru(eta(6)-naphthalene)(eta(4)-bicyclo[3.3.1]nona-2,6-diene)] (1b). As an application of this method, a pesticide lead, 2-methyl-3-(tetrahydrofuran-3-yl)propanamide (6ab) is prepared in 2 steps from 2,5-dihydrofuran in 62% total yield.