Visible Light‐Induced N‐Heterocyclic Nitrenium‐Catalyzed Deoxygenative Borylation of Acyl Chlorides

Considering the appealing synthetic properties of oxygenous feedstocks and organoboron compounds, direct deoxygenative borylation is a very desirable chemical transformation. Directly converting acyl chlorides into alkylboronates through deoxygenative borylation is an unknown but valuable reaction. Herein, a relatively straightforward one‐step methodology is reported where the N‐heterocyclic nitrenium (NHN) ion acts as a photocatalyst under visible light to produce benzylboronates directly from aroyl chlorides in the absence of metals or additives. A large variety of aroyl chlorides are well tolerated under the reaction conditions. Mechanistic investigations and density functional theory calculations support that NHN species are involved in the radical formation and the DMAc‐H 2 O/B 2 cat 2 contributes to the formation of alkylboronates.