The catalytic asymmetric addition of alkynylzinc reagents, which were prepared in situ from dimethylzinc and 1-alkynes, to nitrones was achieved by utilizing di(t-butyl) (R,R)-tartrate as a chiral auxiliary to afford the corresponding optically active (R)-N-(alpha-substituted)propargylic hydroxylamines. By the addition of methylzinc salt of a product-like racemic hydroxylamine, enantioselectivity of the N-propargylic hydroxylamines was enhanced up to 96% ee.