title: Zirconium-promoted epoxide rearrangement-alkynylation sequence.
abstract: Additions of terminal alkynes to electrophiles are important transformations in organic chemistry. Generally, activated terminal alkynes react with epoxides in an S(N)2 fashion to form homopropargylic alcohols. We have developed a new synthetic method to form propargylic alcohols from epoxides and terminal alkynes via 1,2-shifts. This method involves cationic zirconium acetylides as both the activator of epoxides and nucleophiles. Due to the mild conditions to pre-activate alkynes with silver nitrate, this synthetic method is useful for both electron-rich and electron-deficient alkynes with other acid- and base-sensitive functional groups.
authors.affiliation: Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
authors.forename: Brian J
authors.initials: BJ
authors.lastname: Albert
authors.forename: Kazunori
authors.initials: K
authors.lastname: Koide
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D020005:Propanols / Q000737:chemistry; D015040:Zirconium / Q000737:chemistry*
chemical_list: D000480:Alkynes; D004852:Epoxy Compounds; D020005:Propanols; D015040:Zirconium; C028255:propargyl alcohol