Few‐layer Black Phosphorous Catalyzes Radical Additions to Alkenes Faster than Low‐valence Metals

The substitution of catalytic metals by p‐block main elements has a tremendous impact not only in the fundamentals but also in the economic and ecological fingerprint of organic reactions. Here we show that few‐layer black phosphorous (FL‐BP), a recently discovered and now readily available 2D material, catalyzes different radical additions to alkenes with an initial turnover frequency (TOF(0)) up to two orders of magnitude higher than representative state‐of‐the‐art metal complex catalysts at room temperature. The corresponding electron‐rich BP intercalation compound (BPIC) KP(6) shows a nearly twice TOF(0) increase with respect to FL‐BP. This increase in catalytic activity respect to the neutral counterpart also occurs in other 2D materials (graphene vs. KC(8)) and metal complex catalysts (Fe(0) vs. Fe(2−) carbon monoxide complexes). This reactive parallelism opens the door for cross‐fertilization between 2D materials and metal catalysts in organic synthesis.