Assessment of Popular DFT and Semiempirical Molecular Orbital Techniques for Calculating Relative Transition State Energies and Kinetic Product Distributions in Enantioselective Organocatalytic Reactions

Schenker, Sebastian; Schneider, Christopher; Tsogoeva, Svetlana B.; Clark, Timothy

doi:10.1021/ct2002013

Cited by 80 publications

(72 citation statements)

References 51 publications

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“…The results are summarized in Table 1, from which it can be concluded that the best correlation between the benchmark CCSD(T)/def2‐QZVP+COSMO‐RS23 values and the tested DFT functionals was obtained for the ωB97xd/cc‐pVTZ method in combination with the SMD24 solvation model (Table 1). In line with the studies by Clark and Tsogoeva,23e performing the geometry optimization with the ωB97xd/cc‐pVDZ method turned out to afford a better correlation with the CCSD(T) data than that attained by using the B3LYP/6‐31 g(d,p) method (compare methods A and D , Table 1). Therefore, (ωB97xd/cc‐PVTZ+SMD)//(ωB97xd/cc‐PVDZ+SMD) was employed as the method of choice for further calculations.…”

Section: Resultssupporting

confidence: 76%

Cross‐Aldol Reaction of Isatin with Acetone Catalyzed by Leucinol: A Mechanistic Investigation

Kabeshov

Kysilka

Rulı́s̆ek

et al. 2015

Chemistry A European J

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Protein‐metal interactions—traditionally regarded for roles in metabolic processes—are now known to enhance the performance of certain biogenic materials, influencing properties such as hardness, toughness, adhesion, and self‐healing. Design principles elucidated through thorough study of such materials are yielding vital insights for the design of biomimetic metallopolymers with industrial and biomedical applications. Recent advances in the understanding of the biological structure–function relationships are highlighted here with a specific focus on materials such as arthropod biting parts, mussel byssal threads, and sandcastle worm cement.

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Section: Resultssupporting

confidence: 76%

Cross‐Aldol Reaction of Isatin with Acetone Catalyzed by Leucinol: A Mechanistic Investigation

Kabeshov

Kysilka

Rulı́s̆ek

et al. 2015

Chemistry A European J

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“…The merits of ωB97X-D in organocatalytic modeling have also been established in an extensive benchmark study by Clark and co-workers [78]. …”

Section: Methodsmentioning

confidence: 99%

On the possibility to accelerate the thermal isomerizations of overcrowded alkene-based rotary molecular motors with electron-donating or electron-withdrawing substituents

Oruganti

Durbeej

2016

J Mol Model

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We employ computational methods to investigate the possibility of using electron-donating or electron-withdrawing substituents to reduce the free-energy barriers of the thermal isomerizations that limit the rotational frequencies achievable by synthetic overcrowded alkene-based molecular motors. Choosing as reference systems one of the fastest motors known to date and two variants thereof, we consider six new motors obtained by introducing electron-donating methoxy and dimethylamino or electron-withdrawing nitro and cyano substituents in conjugation with the central olefinic bond connecting the two (stator and rotator) motor halves. Performing density functional theory calculations, we then show that electron-donating (but not electron-withdrawing) groups at the stator are able to reduce the already small barriers of the reference motors by up to 18 kJ mol−1. This result outlines a possible strategy for improving the rotational frequencies of motors of this kind. Furthermore, exploring the origin of the catalytic effect, it is found that electron-donating groups exert a favorable steric influence on the thermal isomerizations, which is not manifested by electron-withdrawing groups. This finding suggests a new mechanism for controlling the critical steric interactions of these motors.Graphical AbstractThe introduction of electron-donating groups in one of the fastest rotary molecular motors known to date is found to reduce the free-energy barriers of the thermal steps that limit the rotational frequencies by up to 18 kJ mol−1.Electronic supplementary materialThe online version of this article (doi:10.1007/s00894-016-3085-y) contains supplementary material, which is available to authorized users.

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“…Density functional theory (DFT) methods represent a viable alternative for elucidating the kinetics and mechanisms of atmospheric chemistry processes, due to their excellent performance‐to‐cost ratio . Thus far, many functionals have been developed, each with merits and drawbacks.…”

Section: Introductionmentioning

confidence: 99%

Benchmarking of DFT functionals for the kinetics and mechanisms of atmospheric addition reactions of OH radicals with phenyl and substituted phenyl‐based organic pollutants

Xie

Chen

2017

Int J of Quantum Chemistry

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•OH addition reactions play a pivotal role in the atmospheric transformation of a number of phenyl and substituted phenyl‐based persistent and toxic organic pollutants. Here, we screened appropriate DFT functionals to predict reaction mechanisms and rate constants (kOH) of the •OH additions by taking benzene and substituted benzenes (C6H5F, C6H5Cl, C6H5Br, C6H5CH3, C6H5OH) as model compounds. By comparing the kOH values calculated with DFT methods to experimental values, we found that the ωB97 functional is the best among the 18 functionals considered (using the basis sets 6‐31 + G(d,p) for optimizations and 6‐311++G(3df,2pd) for single point energy calculations) in the temperature range of 230‐330 K. In addition, we found that some other functionals performed well in specific conditions, e.g., BMKD3 is good for benzene, halogenated benzenes and C6H5CH3, and CAM‐B3LYP is good for the reaction of C6H5OH at room temperature. Based on the diversity of the electronic structures of the selected model compounds and the frequent occurrence of certain substituents (CH3, OH, F, Cl, and Br) in the target compounds, the functionals recommended here can be used for future study of the reaction mechanisms and kOH values for •OH addition to phenyl and substituted phenyl‐based persistent and toxic organic pollutants.

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Assessment of Popular DFT and Semiempirical Molecular Orbital Techniques for Calculating Relative Transition State Energies and Kinetic Product Distributions in Enantioselective Organocatalytic Reactions

Cited by 80 publications

References 51 publications

Cross‐Aldol Reaction of Isatin with Acetone Catalyzed by Leucinol: A Mechanistic Investigation

Cross‐Aldol Reaction of Isatin with Acetone Catalyzed by Leucinol: A Mechanistic Investigation

On the possibility to accelerate the thermal isomerizations of overcrowded alkene-based rotary molecular motors with electron-donating or electron-withdrawing substituents

Benchmarking of DFT functionals for the kinetics and mechanisms of atmospheric addition reactions of OH radicals with phenyl and substituted phenyl‐based organic pollutants

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