Ti-catalyzed regioselective ring-opening alkynylation of epoxides with haloalkynes

[Display omitted] •Ti-catalyzed ring-opening alkynylation of epoxides with haloalkynes.•Aromatic or aliphatic terminal epoxides and internal epoxides are suitable substrates.•Mild reaction conditions, broad substrate scope, and good functional group compatibility.•Chemospecificity in the rearrangements of epoxides into aldehydes. Ti-catalyzed ring-opening alkynylation of epoxides with haloalkynes has been achieved, allowing an efficient and regioselective entry to various propargylic alcohols in moderate to good yields. The developed protocol features extremely mild reaction conditions, broad substrate scope, varied functional group compatibility, and chemospecificity in the rearrangements of epoxides to aldehydes.