Quantum dots enable direct alkylation and arylation of allylic C(sp3)–H bonds with hydrogen evolution by solar energy

Summary Direct alkylation and arylation of allylic C(sp3)–H bonds are straightforward approaches for accessing allylic C–C products. However, the engagement of allylic C–C bond-forming reaction without introducing extraneous functional groups and stoichiometric oxidant or reductant has proved difficult. Here, we report a general and mild strategy using semiconductor quantum dots (QDs) as photocatalysts for coupling a broad range of available allylic C(sp3)–H bonds with α-amino C–H bonds or heteroarenes, respectively, under sunlight irradiation (> 85 examples). The protocol bypasses stoichiometric oxidant or reductant and pre-functionalization of both the coupling partners and produces hydrogen (H2) as the byproduct. The outstanding efficiency and selectivity and step- and atom-economy represents the first direct alkylation and arylation of allylic C(sp3)–H bonds with hydrogen evolution powered by solar energy.