Recent Advances in Terminal Alkyne‐Involved Alkynylation and Alkynylation‐Triggered Tandem Reactions

Substituted internal alkynes are one of the most important functional groups in organic chemistry, with broad applications ranging from biochemistry to material science, medicinal chemistry, and pharmaceutical research. Much effort has been made to explore efficient methodologies to introduce an alkyne moiety into molecules. Among alkynylation reagents, terminal alkynes are considered to be the ideal one compared to other substrates like halogenated alkynes and alkynyl hypervalent iodine since it avoids multistep synthesis of these substrates from terminal alkynes to meet the atom‐economy criteria. In this review, we summarized recent achievements (from 2020 to 2025) in the application of terminal alkynes for the alkynylation to afford substituted internal alkynes and alkynylation‐triggered tandem reactions to yield carbo‐ and heterocycles, which exist abundantly in nature as synthetic drugs and biologically active natural and non‐natural products.