Palladium-Catalyzed [3,3]-Rearrangement for the Facile Synthesis of Allenamides

Abstract

A [3,3]-rearrangement that is used for facile construction of chiral allenamides is described. A propargylic alcohol, a chlorophosphite, and Cbz-azide are combined to provide a propargylic phosphorimidate that, in the presence of catalytic palladium(II), rearranges to an allenamide. By varying the substitution pattern on the propargylic alcohol, mono-, di-, and trisubstituted allenamides can be accessed in good yields. Additionally, the use of an enantiomerically enriched propargylic alcohol enables the preparation of stereochemically defined allenamides.