The Hydrolysis Mechanism of Formamide Revisited: Comparison Between ab initio, Semiempirical and DFT Results

Antonczak, Serge; Ruiz‐López, Manuel F.; Rivail, Jean‐Louis

doi:10.1007/s008940050061

Cited by 47 publications

(65 citation statements)

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“…It has already been used for this reaction [43] and is quite similar to that used in CPMD simulations. [17,45] Previous calculations have shown that B3LYP/6-31G(d)-derived geometries are suitable although the interaction energies may include significant errors [40] (see Table 1). For this reason, single-point energy calculations on DFT geometries have been performed at the MP2/6-311 + G** level of theory.…”

Section: Methodsmentioning

confidence: 98%

“…concerted non-assisted MP2/6-31G**//HF/3-21G DE = 42.0 [41] DG = 53.0 MP2/6-31G**//HF/4-31G DE = 44.3 [11] MP2/6-311G**//HF/6-31G* DE = 42.5 [42] DG = 57.2 MP2/6-31G** DE = 40.9 [40] B3LYP/6-31G** DE = 32.7 [40] DG = 44.6 stepwise non-assisted MP2/6-31G**//HF/3-21G DE = 42.1, 38.9 [41] DG = 52.7, 50.4 MP2/6-31 + G** DH = 45.1, 45.4…”

Section: Theoretical Levelmentioning

confidence: 95%

“…[b] [44] MP2/6-311G**//HF/6-31G* DE = 41.1, 38.4 [42] DG = 54.2, 53.1 concerted assisted MP2/6-31G**//HF/3-21G DE = 25.8 [12] DG = 49.6 MP2/6-31G** DE = 31.7 [40] B3LYP/6-31G** DE = 12.6 [40] DG = 36.5 stepwise assisted MP2/6-31 + G** DH = 37.2, 32.5…”

Section: Theoretical Levelmentioning

confidence: 99%

“…Nevertheless, some authors have studied the neutral hydrolysis reaction by assuming that gas-phase processes operate. The hydrolysis of formamide has previously been studied by Krug et al [11] and by Antonczak et al [12,40] The inverse reaction was also considered by Oie et al [41] and by Jensen et al [42] Further calculations have been reported since. [15,17,[43][44][45][46] Here, we briefly summarize the computations made on the uncatalyzed reaction, although the original references should be consulted for further details on the mechanisms of amide hydrolysis.…”

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confidence: 92%

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The Mechanism of Formamide Hydrolysis in Water from Ab Initio Calculations and Simulations

Gorb

Asensio

Tuñón

et al. 2005

Chemistry A European J

109

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Chemical Matching: C2‐ or C3‐alkynylated furans were selectively synthesized by using gold catalysis. Direct C–H alkynylation of furans was achieved with C2 selectivity, and a domino cyclization/alkynylation process starting from allenes gave C3‐alkynylated products. The exact matching of the structure of the gold catalyst and an electrophilic hypervalent iodine reagent was essential for success.

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Section: Methodsmentioning

confidence: 98%

Section: Theoretical Levelmentioning

confidence: 95%

Section: Theoretical Levelmentioning

confidence: 99%

mentioning

confidence: 92%

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The Mechanism of Formamide Hydrolysis in Water from Ab Initio Calculations and Simulations

Gorb

Asensio

Tuñón

et al. 2005

Chemistry A European J

109

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“…for the proton transfer from the H 3 O + moiety of P5-hydro + to the outer water phase, according to Equation (6). As shown in Figures 5 and 7, the acid-catalyzed hydrolysis of TA2 is more favourable than that of TA1, both dynamically and thermodynamically.…”

mentioning

confidence: 97%

Acid‐Catalyzed Reactions of Twisted Amides in Water Solution: Competition between Hydration and Hydrolysis

Wang¹,

Cao²

2011

Chemistry A European J

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The acid-catalyzed reactions of twisted amides in water solution were investigated by using cluster-continuum model calculations. In contrast to the previous widely suggested concerted hydration of the C=O group, our calculations show that the reaction proceeds in a practically stepwise manner, and that the hydration and hydrolysis channels of the C-N bond compete. The Eigen ion (H(3)O(+)) is the key species involved in the reaction, and it modulates the hydration and hydrolysis reaction pathways. The phenyl substitution in the twisted amide not only activates the N-CO bond, but also stabilizes the hydrolysis product through n(N)→π(phenyl) delocalization, leading exclusively to the hydrolysis product of the ring-opened carboxylic acid. Generally, the twisted amides are more active than the planar amides, and such a rate acceleration results mainly from the increase in exothermicity in the first N-protonation step; the second step of the nucleophilic attack is less affected by the twisting of the amide bond. The present results show good agreement with the available experimental observations.

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Radiofrequency ablation

Tanabe

Curley

Dodd

et al. 2004

Cancer

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The acid‐catalyzed reactions of twisted amides in water solution were investigated by using cluster‐continuum model calculations. In contrast to the previous widely suggested concerted hydration of the CO group, our calculations show that the reaction proceeds in a practically stepwise manner, and that the hydration and hydrolysis channels of the CN bond compete. The Eigen ion (H3O+) is the key species involved in the reaction, and it modulates the hydration and hydrolysis reaction pathways. The phenyl substitution in the twisted amide not only activates the NCO bond, but also stabilizes the hydrolysis product through nN→πphenyl delocalization, leading exclusively to the hydrolysis product of the ring‐opened carboxylic acid. Generally, the twisted amides are more active than the planar amides, and such a rate acceleration results mainly from the increase in exothermicity in the first N‐protonation step; the second step of the nucleophilic attack is less affected by the twisting of the amide bond. The present results show good agreement with the available experimental observations.

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The Hydrolysis Mechanism of Formamide Revisited: Comparison Between ab initio, Semiempirical and DFT Results

Cited by 47 publications

References 2 publications

The Mechanism of Formamide Hydrolysis in Water from Ab Initio Calculations and Simulations

The Mechanism of Formamide Hydrolysis in Water from Ab Initio Calculations and Simulations

Acid‐Catalyzed Reactions of Twisted Amides in Water Solution: Competition between Hydration and Hydrolysis

Radiofrequency ablation

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