Saccharin is a versatile scaffold to build up different heterocycles with relevance in asymmetric catalysis, agricultural chemistry, medicinal chemistry, etc. Here, we report a photochemical strategy to obtain seven-member ring benzosultams in one step, using saccharin anion as staring material. The reaction can be improved in a photo-flow reactor and its scope was evaluated. Furthermore, computational study at the CASPT2//CASSCF level of theory was also performed in order to rationalize the involved mechanism.
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