Abstract
Due to the high bond dissociation enthalpies (BDE) of the C–F bond, defluorinative functionalization of CF 3 groups via the formation of fluoroalkyl radicals is a long-standing challenge in organic synthesis. In a recent paper published in JACS, Molander and co-workers described a powerful photochemical defluorinative functionalization of polyfluorinated carbonyls via spin-center shift (SCS). The key to success was a rationally designed photochemical HAT-mediated formation of CO 2 •− and utilization of the reducing power of CO 2 •− to accomplish the reduction of challenging substrates that are centered around the ability of alkyl thiol catalysts to shuttle hydrogen atoms.
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