title: Density Functional and Kinetic Monte Carlo Study of Cu-Catalyzed Cross-Dehydrogenative Coupling Reaction of Thiazoles with THF.
abstract: Cu-catalyzed cross-dehydrogenative coupling (CDC) reaction of thiazoles with THF has been studied with the density functional theory method and kinetic Monte Carlo (kMC) simulations. Our results show that the previously proposed concerted metalation-deprotonation mechanism is unfavorable. On the basis of the DFT calculation and kMC simulation results, a new mechanism is proposed. In the favorable mechanism, the Cu(II) catalyst first combines with the thiazoles, forming an organocopper species that then binds to the THF radical. The rate-limiting step, C-C bond formation, is realized through an intramolecular structural rearrangement. The Cu catalyst works as a matchmaker to render the C-C bond formation. Kinetic Monte Carlo simulations demonstrate that one should be careful with the conclusions drawn simply from the calculated barriers.
authors.affiliation: Key Laboratory of Mesoscopic Chemistry of MOE, Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, P. R. China.
authors.forename: Yuping
authors.initials: Y
authors.lastname: Cai
authors.affiliation: Key Laboratory of Mesoscopic Chemistry of MOE, Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, P. R. China.
authors.forename: Sheng'en
authors.initials: S
authors.lastname: Zhang
authors.affiliation: Key Laboratory of Mesoscopic Chemistry of MOE, Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, P. R. China.|School of Pharmacy, Xuzhou Medical College , No. 209, Tongshan Road, Xuzhou 221004, P. R. China.
authors.forename: Yunsheng
authors.initials: Y
authors.lastname: Xue
authors.affiliation: Center for Multimolecular Chemistry, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, P. R. China.
authors.forename: Juli
authors.initials: J
authors.lastname: Jiang
authors.affiliation: Key Laboratory of Mesoscopic Chemistry of MOE, Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, P. R. China.
authors.forename: Zhao-Xu
authors.initials: ZX
authors.lastname: Chen