title: Fast oxy-cope rearrangements of bis-alkynes: competition with central C-C bond fragmentation and incorporation in tunable cascades diverging from a common bis-allenic intermediate.
abstract: Fast anionic oxy-Cope rearrangements of 1,5-hexadiyn-3,4-olates can be incorporated into cascade transformations which rapidly assemble densely functionalized cyclobutenes or cyclopentenones via a common bis-allenic intermediate. The competition between fragmentation, 4π-electrocyclic closure, and aldol condensation can be efficiently controlled by the nature of the acetylenic substituents. The rearrangement of bis-alkynes with two hydroxyl substituents opens a conceptually interesting entry in the chemistry of ε-dicarbonyl compounds and suggests a new approach to analogues of rocaglamide/aglafolin.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, United States.
authors.forename: Runa
authors.initials: R
authors.lastname: Pal
authors.forename: Ronald J
authors.initials: RJ
authors.lastname: Clark
authors.forename: Mariappan
authors.initials: M
authors.lastname: Manoharan
authors.forename: Igor V
authors.initials: IV
authors.lastname: Alabugin