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An efficient, photocatalytic chlorination of alkylarene α‐H groups using NaCl/HCl as a chlorine source has been developed, which involves a radical mechanism under visible‐light (including sunlight) conditions. A chlorine radical is proposed to be formed by an electron transfer from chloride ion to O2 in air through the bandgap hole of the semiconductor AgCl. The chlorination protocol is characterized...
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