Customized Photoelectrochemical C-N and C-P Bond Formation Enabled by Tailored Deposition on Photoanodes

Photoelectrochemistry (PEC) is burgeoning as an innovative solution to organic synthesis. However, the current PEC systems suffer from limited reaction types and unsatisfactory performances. Herein, we employ efficient BiVO4 photoanodes with tailored deposition layers for customizing two PEC approaches toward C-N and C-P bond formation. Our process proceeds under mild reaction conditions, deploying easily available substrates and ultra-low potentials. Beyond photocatalysis and electrocatalysis, customized PEC offers high efficiency, good functional group tolerance, and substantial applicability for decorating drug molecules, highlighting its promising potential to enrich the synthetic toolbox for broader organic chemistry of practical applications. With customized designs of the deposition layer on the BiVO4 photoanode, two PEC systems were developed for highly efficient catalytic C-N and C-P bond formation. The modified BiVO4@Al2O3 demonstrated substantial performances for important yet challenging coupling between amides and xanthenes under aerobic conditions, whereas BiVO4@Ni1Co7Pi manifested its versatility in C-P coupling between aryl bromides and diphenylphosphine oxide, facilitated by a Ni-catalyzed cycle under ultralow potentials. image