Visible Light‐Enabled sp3‐C−H Functionalization with Chloro‐ and Bromoalkynes: Chemoselective Route to Vinylchlorides or Alkynes

Abstract An unprecedented direct atom‐economic chemo‐ and regioselective hydroalkylation of chloroalkynes and an sp 3 ‐C−H alkynylation of bromoalkynes was achieved. The reaction partners are unfunctionalized ethers, alcohols, amides, and even non‐activated hydrocarbons. We found that a household fluorescent bulb was able to excite a diaryl ketone, which then selectively abstracts a H‐atom from an sp 3 ‐C−H bond. The product of a formal alkyne insertion into the sp 3 ‐C−H bond was obtained with chloroalkynes, providing valuable vinyl chlorides. The photo‐organocatalytic hydrogen atom transfer strategy gives rise to a broad range of diversely functionalized olefins. When bromoalkynes are applied in the presence of a base, a chemoselectivity switch to an alkynylation is observed. This reaction can even be performed for the alkynylation of unactivated sp 3 ‐C−H bonds, in this case with a preference of the more substituted carbon. Accompanying quantum chemical calculations indicate a vinyl radical intermediate with pronounced linear coordination of the carbon radical center, thus enabling the formation of both diastereoisomers after H‐atom abstraction, suggesting that the ( Z )‐diastereoisomer is preferred, which supports the experimentally observed ( E / Z )‐distribution.