Density Functional and Kinetic Monte Carlo Study of Cu-Catalyzed Cross-Dehydrogenative Coupling Reaction of Thiazoles with THF

Autor:	Sheng’en Zhang, Yuping Cai, Zhaoxu Chen, Yun-Sheng Xue, Juli Jiang
Rok vydání:	2016
Předmět:	Coupling 010405 organic chemistry Chemistry Organic Chemistry Bond formation 010402 general chemistry 01 natural sciences Coupling reaction 0104 chemical sciences Catalysis Computational chemistry Intramolecular force Density functional theory Kinetic Monte Carlo
Zdroj:	The Journal of Organic Chemistry. 81:1806-1812
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.5b02503
Popis:	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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::30291f727acb86ff62dafde6830f6ade https://doi.org/10.1021/acs.joc.5b02503 Zobrazit plný text záznamu