A Frontier Molecular Orbital Theory Approach to Understanding the Mayr Equation and to Quantifying Nucleophilicity and Electrophilicity by Using HOMO and LUMO Energies

Zhuo, Lian‐Gang; Liao, Wei; Yu, Zhi‐Xiang

doi:10.1002/ajoc.201200103

Cited by 172 publications

(103 citation statements)

References 74 publications

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“…Such a decrease in LUMO energy can cautiously be understood in terms of increased electrophilicity. 128 The different activities, which might correspond to distinct activity states in line with ndings of Zhao and Chen, 29 were found to be easier to distinguish at 1 mol% Au catalyst loading (Fig. 5, top), decelerating the reaction in so much as to allow for an OFF-ON-OFF-ON switching sequence.…”

Section: Redox-switchable Gold(i) Catalysismentioning

confidence: 85%

Triple the fun: tris(ferrocenyl)arene-based gold(i) complexes for redox-switchable catalysis

et al. 2020

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Section: Redox-switchable Gold(i) Catalysismentioning

confidence: 85%

Triple the fun: tris(ferrocenyl)arene-based gold(i) complexes for redox-switchable catalysis

et al. 2020

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“…In addition, the charge populated on C4 atom in M3 is −0.298 e , revealing that the polarity of C4 atom is reversed to that in the reactant R1 (0.061 e ), which can explain “umpolung” of reactant under the organocatalytic condition. Furthermore, GRI analysis (for details see ESI) has confirmed that the organophosphine strengthens the nucleophilicity of R1 and works as a Lewis base catalyst. As concerned as above, the results of NBO analysis reveal that the organophosphine plays as a bifunctional organocatalyst in this novel [3 + 3] cycloaddition reaction.…”

Section: Resultsmentioning

confidence: 95%

Theoretical investigation toward organophosphine‐catalyzed [3 + 3] annulation of Morita–Baylis–Hillman carbonates with azomethine imines: Mechanism, origin of stereoselectivity, and role of catalyst

Zhang

Qiao

Wang

et al. 2017

Int J of Quantum Chemistry

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A computational study on the detailed mechanism and stereoselectivity of the chiral phosphinecatalyzed C(sp 2 )AH activation/[3 1 3] annulation between Morita-Baylis-Hillman (MBH) carbonates and C,N-cyclic azomethine imines has been performed. Generally, the catalytic cycle consists of two stages, that is, C(sp 2 )AH activation companied by the dissociation of the t-BuOCO 2 2 group forming phosphonium enolate, and [3 1 3] cycloaddition process followed by regeneration of the catalyst. The calculated results indicate that C(sp 2 )AH activation is ratedetermining while [3 1 3] cycloaddition is stereoselectivity-determining. Furthermore, the advantageous hydrogen bond interactions and less steric hindrance in the RR configurational CAC bond forming transition states should be responsible for the favorability of RR-configured product among the four possible products. The special role of the organocatalyst was also identified by natural bond orbital (NBO) and global reactivity index (GRI) analyses. The mechanistic insights obtained in the present study should be useful for understanding the novel organocatalytic C (sp 2 )AH activation and cycloaddition cascade reaction of MBH carbonates, and thus provide valuable clues on rational design of efficient organocatalysts for the C(sp 2 )AH activation/ functionalizations. K E Y W O R D S [3 1 3] cycloaddition, DFT, organophosphine catalysis, stereoselectivity Int J Quantum Chem. 2017;117:e25367.

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“…Here, k B and h are Boltzmann and Planck constants, respectively,

Δ_{r}^{\neq} S_{m}^{θ} (p^{θ})

and

Δ_{r}^{\neq} H_{m}^{θ} (p^{θ})

are standard molar entropy and standard molar enthalpy of activation at the condition of

p^{θ}

=100kPa, respectively, n is the sum of computation coefficient for all reactants …”

Section: Resultsmentioning

confidence: 99%

Theoretical study on the formation mechanisms, dynamics and the effective catalysis of the nitrophenols

Jia

Bai

et al. 2018

ChemistrySelect

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The hydrogen abstraction reactions of mono‐substituted phenols and nitrogen dioxide may be the sources of HONO and phenoxy radical. Further addition reaction of NO2 and phenoxy radical can form 2‐nitrophenol (2‐NP) and 4‐nitrophenol (4‐NP). The specific formation mechanisms and dynamics of NPs have drawn significant attention in recent days. The promoted reaction mechanisms by water, phenol and intermediate have also been studied. Compared with the naked reaction, the catalytic pathways can reduce the energy barrier from 48.40 kcal/mol to 18.23, 23.03 and 18.87 kcal/mol to form 2‐NP, respectively. Water molecules are the most effective catalysts, and the energy barrier could be further reduced to 8.20 kcal/mol when three water molecules are participating in the reaction. Water molecules can not only promote the formation of 4‐NP, but also simplify the reaction steps. In general, the water molecules serve as catalysts in the formation of NPs. The rate constants of 2‐NP and its hydrates have been predicted. The results are listed as follows: k2‐NP =3.82×10−13; k2‐NP‐1W =2.43×10−7; k2‐NP‐2W =3.39×10−4 cm3molecule−1s−1. The rate constants of mono‐substituted phenols (methylamino phenol, aminophenol and hydroquinone) and NO2 are also predicted by the traditional transitional state theory and variational transition state theory using the B3LYP/6‐311++G(3df,3pd)//6‐311++G(d). For the most dominant path, the rate constants for o/m/p‐methylaminophenol are 1.91×10−14, 4.28×10−20 and 8.78×10−15 cm3molecule−1s−1, respectively.

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A Frontier Molecular Orbital Theory Approach to Understanding the Mayr Equation and to Quantifying Nucleophilicity and Electrophilicity by Using HOMO and LUMO Energies

Abstract: in Chinese: 338 www.AsianJOC.org

Cited by 172 publications

References 74 publications

Triple the fun: tris(ferrocenyl)arene-based gold(i) complexes for redox-switchable catalysis

Triple the fun: tris(ferrocenyl)arene-based gold(i) complexes for redox-switchable catalysis

Theoretical investigation toward organophosphine‐catalyzed [3 + 3] annulation of Morita–Baylis–Hillman carbonates with azomethine imines: Mechanism, origin of stereoselectivity, and role of catalyst

Theoretical study on the formation mechanisms, dynamics and the effective catalysis of the nitrophenols

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