Computational Study for the Reaction Mechanism of N-Hydroxyphthalimide-Catalyzed Oxidative Cleavage of Alkenes

Abstract

A computational study of N-hydroxyphthalimidecatalyzed aerobic oxidative cleavage of alkenes is carried out employing density functional theory and high-level coupled-cluster methods, such as coupled-cluster singles and doubles with perturbative triples [CCSD(T)]. Our results demonstrate that the reaction proceeds through the alkoxyl radicals, as opposed to the mechanism suggested by Jiao and co-workers (Org. Lett. 2012, 14, 4158−4161), in which the reaction proceeds via formation of the dioxetane ring. The barriers for the formation of dioxetane derivatives are computed to be higher than 50 kcal mol −1 , while the barriers for the formation of alkoxyl radicals are as low as 13 kcal mol −1 . Our results also demonstrate that epoxide derivatives can be formed as intermediates or byproducts under the reaction conditions.

Reaction mechanism of the green synthesis of glutaric acid

“…We also used Gaussian to perform theoretical calculations on the reaction process and evaluate the reaction pathway by comparing the energy required to form a transition state during the reaction process. [30][31][32][33][34] The difference in reaction mechanism is mainly in the ring-opening reaction of 1,2-epoxide; thus, only the calculation of the process is performed. The acidic ring-opening reaction mechanism of 1,2-epoxide is shown in Scheme 4.…”

Neosilyllithium‐Catalyzed Hydroboration of Alkynes and Alkenes in the Presence of Pinacolborane (HBpin)

“…Furthermore, DLPNO-CCSD(T) calculations with TightPNO settings were carried out on the DFT optimized structures to determine the accurate energetics of the reaction. [35][36][37] (see Supporting information for details on Computational Methods). The DLPNO-CCSD(T) computed free energy profile pathway is provided in Figure 2.…”