Yang, GuoqiangWu, HuaGallarati, SimoneCorminboeuf, ClémenceWang, QianZhu, Jieping2022-08-172022-08-172022-08-172022-08-0210.1021/jacs.2c06578https://infoscience.epfl.ch/handle/20.500.14299/190157Directly editing an all-carbon quaternary carbon itself of nonstrained acyclic molecules remains underexploited despite the recent advances in the fields of both C–H and C–C bond activation. Herein, we report a palladium-catalyzed migrative carbofluorination of saturated amides enabled by the activation of both the C(sp3)–H and the Cquaternary–Cσ bonds. In this transformation, the α-quaternary carbon of Weinreb amides is converted to α-tertiary fluoride with concurrent migration of an aryl or an amido group from the α- to β-carbon. DFT calculations indicate that the dyotropic rearrangement proceeds through an unusual anti-selective [2.1.0] bicyclic transition state. The reaction, compatible with a broad range of functional groups, is stereospecific and is applicable to the synthesis of enantioenriched products.text::journal::journal article::research article