Direct enantioselective α-amination of amides guided by DFT prediction of E/Z selectivity in a sulfonium intermediate

Chiral amines are a highly important class of compounds for which powerful synthetic approaches remain in high demand. Herein, we report an unprecedented method the preparation chiral α-amino amides from cheap and abundant starting materials. Our strategy relies on direct amination using enantiopure sulfinamides. It involves [2,3]-sigmatropic rearrangement key sulfonium intermediate. We further show how quantum chemical calculations allow predictive insights into critical E/Z selectivity this amino-vinyloxy-sulfonium species.