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

J Org Chem. 2010 Dec 17;75(24):8689-92. doi: 10.1021/jo101838a. Epub 2010 Nov 23.

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.