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

Direct alkylation and arylation of allylic C(sp3)-H bonds are straight-forward 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(sp(3))-H bonds with alpha- 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 (H-2) as the byproduct. The outstanding efficiency and selectivity and step- and atom-economy represents the first direct alkylation and arylation of allylic C(sp(3))-H bonds with hydrogen evolution powered by solar energy.

Automated summary

The study presents a method using semiconductor quantum dots as photocatalysts to directly couple allylic C(sp(3))-H bonds with alpha-amino C-H bonds or heteroarenes under sunlight irradiation. The protocol does not require additional oxidants or reductants, pre-functionalization of coupling partners, and produces hydrogen as a byproduct. This represents the first direct alkylation and arylation of allylic C(sp(3))-H bonds with hydrogen evolution powered by solar energy, showcasing outstanding efficiency, selectivity, step- and atom-economy.