Scheme 3. Sequential ortho- and meta-C–H functionalizations. (a) 5f (2 equiv.), Pd(OAc)2 (10 mol%), Ac-Gly-OH (20 mol%), HFIP (3 equiv.), Ag2CO3 (30 mol%), O2 (1 atm), t-amyl-OH, 24 h, 90 °C, 86% yield; (b) LiHMDS (2.5 equiv.), MeI (3 equiv.), THF, –15 °C, 58% yield (85% yield based on recovered starting material [brsm]); (c) Pd/C (12 mol%), H2 (1 atm), MeOH, 98%; (d) 5e (2 equiv.), Pd(OAc)2 (10 mol%), Ac-Gly-OH (20 mol%), AgOAc (3 equiv.), DCE (1 mL)/HFIP (1 mL), 48 h, 90 °C, N2, 73%.
