As a first demonstration of this concept, we established a benchmark system based on the Pd-catalyzed homologation of arylboronic acid 1 with the methylene donor 2-Br to deliver benzylic BPin product 3 (Table ). Optimization established standard conditions that delivered 3 in good yield with low loadings of a simple Pd catalyst and the mass balance comprising the transesterification adduct 4 (entry 1). 2-Br was completely consumed, which suggested competing hydrolysis to the boronic acid and protodeboronation. This was supported by control experiments (not shown, see ESI). Selected key parameters are indicated in Table . The surprising reactivity of 2-Br was evident from the outset -the reaction required low loadings of Pd(PPh3)4 and attempts to use any more electron-rich phosphine system led to lower yields and increased speciation (e.g., entries 3-4; see ESI for a full ligand screen).