(A) One-pot large-scale synthesis of 5b. Reaction conditions: 8 (10 mmol, 1 equiv.), 9 (10 mmol, 1 equiv.), CuTc (5 mol%), CHCl3 (15 mL), rt, 4 h; then rhodium(II) octanoate (0.1 mol%), 70 °C, 2 h. (B) Functionalization of 5b. a. PhNH2 (3 equiv), MeOH, rt, 6 h; b. 3-azidopropan-1-amine (2 equiv.), MeOH, rt, 2 h; c. hydrazine-hydrate (5 equiv), MeOH, rt, 1 h; d. Phenyl hydrazine hydrochloride (1.1 equiv), MeOH, rt, 5 h; e. Sulfamide (1.1 equiv), p-TsOH (10 mol%), MeOH, 70 °C, 36 h; See supporting information for reaction details.