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Main observation and conclusionrnA method for photoinduced Nal-promoted radical borylation of aliphatic halides and pseudohalides with bis(catecholato)diboron(B2cat2) as the boron source is introduced.The borylation reaction is operationally simple and shows high functional group tolerance and broad substrate scope.Preliminary mechanistic studies suggest that the reaction proceeds through SN2-based radical-generation strategy.