Asymmetric 1,3-rearrangement of an alkynyl group of alkynyl alkenyl carbinols giving beta-alkynylketones took place in high yields with high enantioselectivity in the presence of a hydroxyrhodium/(R )-binap catalyst. The present method including a key beta-alkynyl elimination step in the catalytic cycle is synthetically equivalent to the asymmetric conjugate addition of terminal alkynes to beta-substituted enones.