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A novel and easy‐to‐execute light‐driven protocol for the preparation of alkyl boronic acid pinacol esters from vinyl boronate using N‐hydroxyphthalimide esters as the potential precursor is described. In this photochemical protocol, the N‐hydroxyphthalimide ester's fragmentation generates C‐centered radicals, which undergo a radical Michael addition to vinyl boronic pinacol ester furnishing the desired...