Electron Donor–Acceptor\nComplex-Enabled Autoinductive\nConversion of Acylnitromethanes to Acylnitrile Oxides in a Photochemical\nMachetti–De Sarlo Reaction: Synthesis of 5‑Substituted\n3‑Acylisoxazoles

A photochemical Machetti–De Sarlo reaction has\nbeen developed\nfor preparing 5-substituted 3-acylisoxazoles from acylnitromethanes\nand terminal alkynes. This photochemical protocol utilizes an innovative\nelectron donor–acceptor complex, generated <i>in situ</i> from acylnitromethanes, catalytic LiO<sup><i>t</i></sup>Bu, and 1,1,1,3,3,3-hexafluoro-2-propanol, as a photosensitizer to\npromote rapid conversion with a broad substrate scope in up to 80%\nefficiency. A sigmoidal autoinductive kinetic profile is revealed,\ndemonstrating the novel and unique dual catalysis in the first photochemical\napproach of this reaction.