Translation to 1,1-disubstituted styrenes was tolerated in good yield and diastereoselectivity (5), while electron-rich dienes were also compatible in the ortho, meta and para positions (6 to 8). The incorporation of heterocycles, such as furan, proceeded in good yield resulting in a slight erosion of diastereoselectivity (9). Inductively and mesomerically electron withdrawing motifs were also tolerated in the diene scaffold with little effect on reactivity or selectivity (10 to 14), while modifications of the 1,1-diphenyl ethylene coupling partner were also effective (15). However, to our great surprise, extending the chromophore to a triene system activated an alternative reaction pathway generating an intermolecular 4+2, skipped diene product, whose structure was conclusively determined via x-ray analysis after oxidation. It is pertinent to note at this stage, that any deviation away from styrenyl coupling partners resulted in little to no target reactivity, favoring diene homodimerization (See ESI for full details on unsuccessful substrates). Although our developed protocol enables expedient access to synthetically useful, complex scaffolds that contain a boron and alkene handle, efficiency is contingent on the use of a syringe pump and an excess of styrene to mitigate dimerization. To gain a better understanding of the dimerization process we probed reactivity in the absence of an alkene coupling partner (Scheme 2). It was found that dimerization was rapid leading to 36% conversion (of a possible 50%) after only one hour, which we attribute to aggregation effects in solution (See ESI for full details). At this stage, it was envisaged that increasing steric parameters, or modulating intrinsic reactivity of the participating double bond may be beneficial to enhance the desired reactivity. The incorporation of an additional BPin handle, diene 17, led to no observed homodimerization after one hour indicating its unique ability to mitigate dimerization. X-ray analysis of the geminal BPin diene 17 revealed a more sterically congested system, with one BPin motif in the plane and the other perpendicular, that likely limits aggregation (See ESI for full details). 20