The synthesis of chiral 3-aryl-1-alkynes 3 via cross-coupling of 3-alkyl-and 3, 3-dialkyl-1- bromo-1, 2-dienes 1 and arylbromocuprates (RCuBr) MgBr⊙ LiBr 2 was examined. With phenylcopper reagents and its para-substituted derivatives, as well as with 2-naphthyl cuprates, the reaction gave compounds 3 with high regioselectivity and good yields on the chemically pure product. On the contrary, when ortho-substituted phenyl reagents and 1- ...