Access to α-Functionalized Amines via Calcium-Catalyzed Deacetylations

A calcium-catalyzed approach to accessing α-functionalized amines via deacetylation has been developed. Using Ca(NTf₂)₂/<i>n</i>BuNPF₆ as a mild Lewis acid system, a range of α-acetoxy substrates undergo smooth deacetylation and functionalization. The reaction displays excellent substrate tolerance and accommodates diverse nucleophiles, including sulfur, indole, amide, and cyanide derivatives. Furthermore, telescoped deprotection-reprotection protocols enable facile access to a variety of <i>N</i>-protected amines in high yields, providing a simple and practical route to valuable α-functionalized amine scaffolds.