Herein, a visible-light photochemical approach for practical helicene functionalization at very mild reaction conditions is described. The photochemical reactions allow for the regiospecific and innate late-stage functionalization of helicenes and are easily executed either through the activation of C(sp2 )-Br bonds in helicenes using K2 CO3 as inorganic base or direct C(sp2 )-H helicene bond functionalization under oxidative photoredox reaction conditions. Overall, using these transformations six different functional groups are introduced to the helicene scaffold through C-C and four different C-heteroatom bond-forming reactions.

Fakultät für Chemie und Pharmazie Universität Regensburg 93040 Regensburg Germany

Institute of Chemical Process Fundamentals of the CAS v v i Rozvojová 2 135 Prague 6 165 02 Czech Republic

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Although the detailed mechanistic pictures of these transformations remain to be elucidated, we anticipate that the photochemical helicene C−Br bond functionalizations reactions proceed through base-promoted activation of C(sp2)−Br bond.

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