Organocatalytic Decarboxylation of 2‐phenylbutanoic Acid and 1,4‐dicyanobenzene: A DFT Investigation

Abstract Mechanisms of photo‐catalytic decarboxylative reaction between 2‐phenylbutanoic acid and 1,4‐dicyanobenzene (1,4‐DCB) have been investigated with the method of M06‐L/ma‐def2‐TZVP in the domain‐decomposition COnductor‐like Screening MOdel (ddCOSMO) of CH 3 CN. The TDDFT calculations of 1,4‐DCB and 2‐phenylbutanoic acid model have revealed the photo‐excitation and electron transfer process, which could agree with experimental phenomena. The computational results of Gibbs free energy profiles show that the R1+1,4‐DCB model could achieve the decarboxylative reaction under the 300 nm UV light in path c. And paths a and b indicate that HPO 4 2− and K 2 HPO 4 could assist the whole reaction process with lower energy barrier successfully. Results would provide valuable insights into these types of interactions and related ones.