(A) Same-excess experiment. (B) Different-excess experiments of starting material and ethyl acrylate. aDue to secondary reaction of ethyl acrylate, same-excess 1 and 2 were set up with amounts of 5c, 7, 6c, 6c’, BQ(0.375 M), and AgOAc (2.250 M) to equal the amounts observed by qNMR at time = 45 min for the standard reaction (see Figure S16 in SI). bReaction conditions unless otherwise stated: 5c (variable), 7 (variable), AgOAc (3 equiv), Benzoquinone (0.5 equiv), Pd(OAc)2 (10 mol%), tAmylOH (1 ml), Boc-L-phenylalanine (0.2 equiv), DMSO (7 equiv), 4Å molecular sieves, 75 °C, air