Enantio- and diastereoselective conjunctive cross-coupling of beta-substituted alkenylboron "ate" complexes is studied. Whereas beta-substitution shifts the chemoselectivity of the catalytic reaction in favor of the Suzuki-Miyaura product, use of a boronic ester ligand derived from acenaphthoquinone allows the process to favor the conjunctive product, even with substituted substrates.