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Abstract The industrial importance of the CC double bond difunctionalization in vegetable oils/fatty acid chains motivates computational studies aimed at helping to improve experimental protocols. The CC double bond epoxidation is studied with hydrogen peroxide, peracetic acid (CH3CO3H), and performic acid (HCO3H) oxidizing agents. The epoxide ring‐opening mechanism is calculated in the presence of ZnCl2, NiCl2, and FeCl2Lewis acidic catalysts. Computations show that H2O2(∆G‡= 39 kcal/mol,TS1HP) is not an effective oxidizing agent compared to CH3CO3H (∆G‡= 29.8 kcal/mol,TS1PA) and HCO3H (∆G‡= 26.7 kcal/mol,TS1PF). The FeCl2(∆G‡= 14.7 kcal/mol,TS1FC) coordination to the epoxide oxygen facilitates the ring‐opening via lower energy barriers compared to the ZnCl2(∆G‡= 19.5 kcal/mol,TS1ZC) and NiCl2(∆G‡= 29.4 kcal/mol,TS1NC) coordination. ZnCl2was frequently utilized as a catalyst in laboratory‐scale procedures. The energetic span model identifies the FeCl2(FC) catalytic cycle as the best option for the epoxide ring‐opening.
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This content will become publicly available on April 7, 2026
Can Water Trigger Room‐Temperature Formation of Benzofuran‐2( 3H )‐one Scaffolds From Vinyldiazene Derivatives? Computational Insights Into an Unusual Cyclization
ABSTRACT Access to benzofuran‐2(3H)‐one derivatives from readily available substrates under mild conditions is crucial in the pharmaceutical and plastics industries. We identified (Z)‐3‐(2‐phenylhydrazineylidene)benzofuran‐2(3H)‐one (P) during the recrystallization of (E)‐2‐(2,2‐dichloro‐1‐(phenyldiazenyl)vinyl)phenol using a 96% ethanol solution. The mechanism of the unexpected substrate conversion leading toPis investigated using density functional calculations. The computations revealed that ethanol is required to initiate the reaction viaTS1E, which involves a concerted deprotonation of ethanol by the basic diaza group of the substrate and an ethoxy group attacking the electrophilic center (Cl2C), with an energy barrier of 28.3 kcal/mol. The resulting intermediate (I1E) is calculated to be unstable and can yield a cyclic chloroacetal adduct with a lower energy barrier of 2.2 kcal/mol via the ring‐closure transition state (TS2E). In the absence of water, the next steps are impossible because water is required to cleave the ether bond, yieldingP. A small amount of water (4% of the recrystallization solvent) can promote further transformation ofI2Evia the transition statesTS3E(∆G‡ = 11.1 kcal/mol) andTS4E(∆G‡ = 10.5 kcal/mol). A comparison of the ethanol/water‐ and only water‐promoted free energy profiles shows that the presence of ethanol is crucial for lowering the energy barriers (by about 5 kcal/mol) for the initial two steps leading to the cyclic chloroacetal (I2E), whereas water is then required to initiate product formation.
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- Award ID(s):
- 2152633
- PAR ID:
- 10582909
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Journal of Computational Chemistry
- Volume:
- 46
- Issue:
- 10
- ISSN:
- 0192-8651
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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