Photocatalytic Functionalization of Heptacyclo[6.6.0.0 2,6 .0 3,13 .0 4,11 .0 5,9 .0 10,14 ]Tetradecane

Abstract

Abstract The regioselective functionalization of heptacyclo[6.6.0.0 2,6 .0 3,13 .0 4,11 .0 5,9 .0 10,14 ]tetradecane (HCTD) under photocatalytic conditions is described. The protocols developed share an initial photo‐triggered hydrogen atom abstraction that regioselectively generates the necessary HCTD‐radical preferentially at position 1‐, they employ no excess of the precious cage carbocycle, and enable the straightforward access to a broad variety of 1‐(alkyl, aryl, or sulfinyl) HCTDs in moderate but still synthetically useful yields. The scope and limitations of each transformation are also discussed.