A Dual Role\nfor the <i>N</i>‑Perfluorobutanesulfinamide\nAuxiliary in an Asymmetric Decarboxylative Mannich Reaction

Herein, we demonstrate that the enhanced electrophilicity\nof <i>N</i>-perfluorobutanesulfinamide auxiliary-derived\nimines enables\na highly selective decarboxylative Mannich reaction under mild conditions.\nThe molecular sieves-mediated transformation tolerates a broad substrate\nscope and produces chiral β-amino thioesters in high yield.\nAdditionally, we demonstrate that the <i>N</i>-perfluoroalkyl\nsulfinyl group can function as a phase tag for fluorous purification,\nthus enabling the rapid isolation of the chiral amine products by\nsolid-phase extraction. The synthetic utility of this method is illustrated\nby the synthesis of sitagliptin, ruspolinone, and the natural product\nnegamycin.