Computational study on the addition of HCN to methanimine catalyzed by formamidine and formamide

Li, Jing; Han, Keli; He, Guo‐Zhong

doi:10.1016/j.theochem.2004.09.054

Cited by 4 publications

(2 citation statements)

References 50 publications

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“…T B3LYP and MP2 methods have given different results for the addition of HCN or HNC methanimine with formamidine. At B3LYP level, a lower intermediate with aminoac tonitrile has been located [17]. It has been [18] found that the addition of three water m ecules giving rise to a ring reaction significantly favors isomerization.…”

Section: Introductionmentioning

confidence: 98%

Theoretical Analysis of the Catalytic Hydrolysis Mechanism of HCN over Cu-ZSM-5

Zhang

Peng

et al. 2022

Catalysts

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HCN catalytic hydrolysis mechanism over Cu-ZSM-5 was investigated based on the density functional theory (DFT) with 6-31++g (d, p) basis set. Five paths (A, B, C, D, and E) were designed. For path A and path B, the first step is the nucleophilic attack of water molecule. Next, the hydrogen atom of H2O is transferred to the nitrogen atom first for path A, while in path B, the hydrogen atom of the HCN is first transferred to the nitrogen atom. In path C, HCN isomerizes to HNC initially, and the remaining steps are similar to that of path A. The H atom of HCN shifts to Cu-ZSM-5 initially in path D, and the H atom is transferred to N atom subsequently. The last step is the attack on water molecule. The first step for path E is similar to that of path D. The next step is the attack on water molecule, in which the H atom of water molecule shifts to N atom, and the H on Cu-ZSM-5 shifts to the N atom. Meanwhile, the H atom of oxygen atom is transferred to the N atom. The results show that path C is the most favorable path, with the lowest free energy barrier (35.45 kcal/mol). The results indicate that the Cu-ZSM-5 strongly reduces the energy barrier of HCN and isomerizes to HNC, making it an effective catalyst for HCN hydrolysis.

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Section: Introductionmentioning

confidence: 98%

Theoretical Analysis of the Catalytic Hydrolysis Mechanism of HCN over Cu-ZSM-5

Zhang

Peng

et al. 2022

Catalysts

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“…Actually, several theoretical studies were reported of the last step of the first reaction stage of the Strecker reaction [ 10 – 16 ], i.e. the hydrocyanation of imines (or protonated imines + CN − ) to aminonitriles.…”

Section: Introductionmentioning

confidence: 99%

Proton transfers in the Strecker reaction revealed by DFT calculations

Yamabe¹,

Zeng²,

Guan³

et al. 2014

Beilstein J. Org. Chem.

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SummaryThe Strecker reaction of acetaldehyde, NH3, and HCN to afford alanine was studied by DFT calculations for the first time, which involves two reaction stages. In the first reaction stage, the aminonitrile was formed. The rate-determining step is the deprotonation of the NH3 + group in MeCH(OH)-NH3 + to form 1-aminoethanol, which occurs with an activation energy barrier (ΔE ≠) of 9.6 kcal/mol. The stereochemistry (R or S) of the aminonitrile product is determined at the NH3 addition step to the carbonyl carbon of the aldehyde. While the addition of CN− to the carbon atom of the protonated imine 7 appears to scramble the stereochemistry, the water cluster above the imine plane reinforces the CN− to attack the imine group below the plane. The enforcement hinders the scrambling. In the second stage, the aminonitrile transforms to alanine, where an amide Me-CH(NH2)-C(=O)-NH2 is the key intermediate. The rate-determining step is the hydrolysis of the cyano group of N(amino)-protonated aminonitrile which occurs with an ΔE ≠ value of 34.7 kcal/mol. In the Strecker reaction, the proton transfer along the hydrogen bonds plays a crucial role.

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Computational study on the mechanism and thermodynamic of atmospheric oxidation of HCN with ozone

Abdollahpour

Vahedpour

2013

Struct Chem

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Computational study on the addition of HCN to methanimine catalyzed by formamidine and formamide

Cited by 4 publications

References 50 publications

Theoretical Analysis of the Catalytic Hydrolysis Mechanism of HCN over Cu-ZSM-5

Theoretical Analysis of the Catalytic Hydrolysis Mechanism of HCN over Cu-ZSM-5

Proton transfers in the Strecker reaction revealed by DFT calculations

Computational study on the mechanism and thermodynamic of atmospheric oxidation of HCN with ozone

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