Reactions of α‑Functionally Substituted Enals with Terminal Alkynes: Unexpected Assembly of 2‑Amino-2-Cyclopentenones

The reactions of α-chalcogen, α-halo, or α-amino functionally substituted enals with terminal alkynes leading either to corresponding propargyl alcohols (for O-, S-, Cl-, and Br-bearing substrates) or unexpected 2-amino-2-cyclopentenones (for aminoenals) are described. The key feature of these reactions is the rearrangement of adducts bearing amino groups on silica gel that triggered further cyclization to five-membered carbocycles.