Reaction of oxabicyclic alkenes with alkynes and organoboronic acids in the presence of Ni(cod)2, P(t-Bu)3, and CsF in a binary solvent toluene–methanol (1 : 3) at 75 to 85°C provided exo-5,6-disubstituted 7-oxanorbornene derivatives in good to excellent yields. © 2013 The Royal Society of Chemistry.