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

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 CH3CN. 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 HPO42- and K2HPO4 could assist the whole reaction process with lower energy barrier successfully. Results would provide valuable insights into these types of interactions and related ones.