New synthetic strategies for the stereocontrolled synthesis of substituted ‘skipped’ diepoxides

Tetrahedron 65(33), 6648-6655, DOI: 10.1016/j.tet.2009.05.074

This report describes a number of new synthetic approaches toward methyl-substituted mono- and diepoxy alcohols that serve as substrates for endo-selective epoxide-opening cascades. The key transformations involve the manipulation of alkynes. Highlighted are the directed methylmetalation of bishomopropargylic alcohols, the bromoallylation of alkynes, and Pd-catalyzed cross-coupling between an alkenyl boronate ester and allylic bromides.