Regio- and Stereocontrolled Hydrohalogenation of Ynamides with -Halosuccinimides (NXS) as the Halogen Source: Synthesis of ()-α-Haloenamides.

Presented herein is a facile stereoselective construction of synthetically versatile chiral and achiral ()-α-haloenamides under mild conditions utilizing -halosuccinimides and diphenylphosphine oxide. This reaction is metal-free, mild, efficient, very rapid, and practical and highlights the synthetic versatility of ynamides. The reaction has a broad substrate scope; both chiral and achiral ynamides have been transformed into the corresponding ()-α-haloenamides within a very short period of time without compromising selectivity or complexity.