title: Tandem Blaise/retro-Blaise reaction for the nitrile-mediated regioselective intermolecular addition of unstabilized zinc ester enolates (Reformatsky reagents) to 1-alkynes and 1,3-enynes.
abstract: We report the novel use of a nitrile as a mediator to achieve the regioselective intermolecular addition of unstabilized zinc ester enolates (Reformatsky reagents) to 1-alkynes and 1,3-enynes. This reaction is made possible by a reversible addition of enolates to a nitrile (Blaise reaction), generating a zinc aza-enolate that, unlike zinc ester enolates, can add intermolecularly to 1-alkynes and 1,3-enynes. Subsequent removal of the nitrile through a retro-Blaise reaction generates the targeted addition product. This method is combined with a Diels-Alder reaction and subsequent oxidative aromatization, providing a tandem one-pot de novo construction of α-arylated alkanoates from Reformatsky reagents.
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University , 120-750 Seoul, Korea.
authors.forename: Ju Hyun
authors.initials: JH
authors.lastname: Kim
authors.forename: Yu Sung
authors.initials: YS
authors.lastname: Chun
authors.forename: Sang-gi
authors.initials: SG
authors.lastname: Lee