Sep 2026· International Journal of Quantum Chemistry· 0 citations· 22 references
Abstract
The influence of the superbase nature on the reaction mechanism of the methanol isopropenylation with a propyne‐allene mixture in the KOH·0.5H
2
O/NMP and KOH/DMSO systems has been studied using a combined quantum chemical approach including DFT methods (B2PLYP‐D2/6–311+G**//B3LYP/6–31+G* + PCM). The superbases are modeled by the pentasolvate complexes KOH·5NMP, KOH·H
2
O·5NMP and KOH·5DMSO. According to the results obtained, the reaction proceeds preferentially via the addition of methoxide ion to allene, and this is the rate‐determining stage. A significant decrease in the yield of the reaction product in the KOH·0.5H
2
O/NMP system (KOH·H
2
O·5NMP complex) compared to KOH/DMSO (KOH·5DMSO complex) is explained by a higher activation barrier associated with the hydration of the attacking nucleophile. The lower activation barrier of the rate‐determining stage obtained in the presence of KOH·5NMP, compared to KOH·5DMSO, shows the competitiveness of the KOH/NMP system over KOH/DMSO in the vinylation of alcohols by propyne‐allene mixture under anhydrous conditions.
Direct propylene epoxidation with H
2
and O
2
over Au/TS‐1 is an attractive alternative for the production of propylene oxide (PO), and acquiring its reaction kinetics is essential for the industrialization of this process. Herein, its intrinsic kinetics are established by using Au/TS‐1‐B with template‐blocked...
Daiyi Yu, Zhihua Zhang, Yang Zheng et al.· AIChE Journal· 0 citations
The development of sustainable methods for the oxidation of alcohols to aldehydes or ketones remains an important goal in synthesis. In this work, we synthesized a series of nitrate‐bearing oxoammonium salts and demonstrated their efficiency as metal‐free catalysts for the aerobic oxidation of alcohols. These catal...
Wan-Qi Sun, Jia-Yi Dong, Zi-Jie Yu et al.· Chinese journal of chemistry· 0 citations
Synthetic studies toward
des
‐thiomethyllooekeyolide A (
5
), involving the convergent synthesis of the C
1
–C
16
polyketide fragment
25
and efforts toward construction of the pyran hemiketal motif, are described. Aldehyde
9
was prepared from butyraldehyde (
11
) via Brown crotylation and Mukaiyama al...
In-Cho Su, Duck Hyung Lee· Bulletin of the Korean Chemi...· 0 citations
Propylene is a key chemical. Propane dehydrogenation (PDH) over non‐noble cobalt catalysts suffers rapid deactivation from sintering and coking. Herein, we report a core–shell catalyst (1.0Co/BEA@
x
Si) with a mesoporous silica shell on Co‐impregnated dealuminated Beta zeolite. The silica shell enhances Co disper...
Yi-Rong Wang, Qin Sun, Junbo Li et al.· AIChE Journal· 0 citations
The B3LYP‐D3/def2‐TZVPP level of theoretical study is performed to examine the stability of pure Ce
2
O
4
and CeMO
4
(M = Ti and Sn) clusters. Adsorption and Co‐adsorption of CO and H
2
O are also carried out on pure and doped clusters. Additionally, global and local reactivity descriptors, as well as natur...
Partha Pratim Churi, Gaurisankar Phukan, Shilpa Neog et al.· International Journal of Qua...· 0 citations
A density functional theory study of CO
2
and the cyclic trimer 1,3,5‐trioxanetrione (C
3
O
6
) coordination to Ni
2+
, Cu
2+
, and Zn
2+
is presented to elucidate how metal identity, ligand topology, and coordination environment govern multiligand binding thermodynamics. In the absence of coordinating...
Puthiyavalappil K. Arathi, Mini Bharati Ahirwar, C. Suresh· International Journal of Qua...· 0 citations
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