Visible-light-driven net-1,2-hydrogen atom transfer of amidyl radicals to access β-amido ketone derivatives
Yonggang Jiang, Hui Li, H. Tang, Qingyue Zhang, Haitao Yang, Yu Pan, Cheng‐Gang Zou, Hongbin Zhang, Patrick J. Walsh, Xiaodong Yang
Abstract
-aryloxy amides generates nitrogen-centered radicals (N˙), which undergo a rare net-1,2-HAT to form carbon-centered radicals (C˙). The C-centered radicals are then captured by silyl enol ethers on the way to β-amido ketones. A series of β-amido ketone derivatives (33 examples, up to 97% yield) were prepared with good functional group tolerance demonstrating the synthetic utility of this method. Mechanistic studies, including EPR, radical trapping experiments, deuterium labeling and KIE measurements, suggest an intramolecular radical net-1,2-HAT pathway.
Topics & Concepts
RadicalHydrogen atomKetoneChemistryNet (polyhedron)PhotochemistryHydrogenVisible spectrumCombinatorial chemistryOrganic chemistryMaterials scienceMathematicsAlkylGeometryOptoelectronicsRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques