Insights into the N-Heterocyclic Carbene (NHC)-Catalyzed Oxidative γ-C(sp<sup>3</sup>)–H Deprotonation of Alkylenals and Cascade [4 + 2] Cycloaddition with Alkenylisoxazoles

Li, Xue; Wang, Yanyan; Wang, Yan; Tang, Mingsheng; Qu, Lingbo; Li, Zhongjun; Wei, Donghui

doi:10.1021/acs.joc.8b01112

Cited by 62 publications

(18 citation statements)

References 105 publications

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“…The population analysis, especially the spin density population analysis along the reaction pathway can provide useful information for the reaction mechanism. [ 54,55 ] To illustrate the radical addition process, the spin density population analysis of some open‐shell molecules along the reaction coordinate is performed and the spin density isosurface graphs are shown in Figure 5.…”

Section: Resultsmentioning

confidence: 99%

Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Kang

Huo

Meng

et al. 2020

Applied Organom Chemis

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Transition metal-catalyzed atom transfer radical addition (ATRA) reactions are an effective and versatile strategy for constructing carbon-carbon bonds in organic synthesis. Typically, the metal center in this metal-assisted radical transformation undergoes a reversible redox process. In this work, a quintuply-bonded dinuclear complex, Mo 2 (N^N) 2 {N^N = μ-κ 2-CH[N(2,6-iPr 2 C 6 H 3)] 2 }, has been investigated as potential catalyst for radical addition of CCl 4 to 1-hexene by performing density functional theory (DFT) calculations. The study shows that the Mo 2 (N^N) 2-mediated radical addition reaction is computationally predicted to occur with acceptable activation energies, indicating that the Mo-Mo quintuple bond can be applied as an effective catalyst for this transformation under mild conditions. The whole reaction involves 3 steps, two of which are metal-mediated. Firstly, the C-Cl bond activiation catalyzed by Mo 2 (N^N) 2 to obtain Mo 2 (N^N) 2 Cl and •CCl 3 radical; Then the •CCl 3 radical interacts with 1-hexene to get an addition, the addition product reacts with the Mo 2 (N^N) 2 Cl to get the last product and regenerate the catalyst Mo 2 (N^N) 2. Both the thermodynamic and kinetic study show that the second step is the rate-determine step. When coordinating solvent pyridine is added to the catalytic reaction, the reaction is suppressed due to their high energies barriers, which is consistent with experimental results.

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Section: Resultsmentioning

confidence: 99%

Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Kang

Huo

Meng

et al. 2020

Applied Organom Chemis

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“…6‐311G(d) basis set for C, O, H atoms and the Los Alamos National Laboratory basis set of double‐ξquality(LANL2DZ) was used for Pd atom. Gaussian 09 has been widely used to clarify the detailed mechanisms of transition metal‐catalyzed and organic catalytic reactions . The convergence criteria using the default values of the Gaussian 09 program.…”

Section: Computational and Theoretical Methodsmentioning

confidence: 99%

Activation Pathway of C‐H and C–C Bonds of Ethane by Pd Atom with CO₂ as a Soft Oxidant

et al. 2019

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Ethane and CO2 can be converted to synthesis (CO and H2) via the dry reforming pathway and formed important industrial raw material ethylene through oxidative dehydrogenation pathway, which are relating to the C−C bond and C−H bond cleavage, respectively. In this study, density functional theory was used to study the activation reaction of ethane C−H bond, C−C bond on Pd atom with CO2 as oxidant. CH3CH3→CH2CH3+H→CH2CH2+2H is the dominant path for dehydrogenation to ethylene. Adding an appropriate amount of H2 can reduce the deep dehydrogenation of ethylene and increase the selectivity. Under the condition of 873 K with Pd atom as catalyst, it is more inclined to ethane/CO2 reforming reaction. The main route for generating CO is CH3CH2+H→CH3+CH3→CH2→CHOH→CHO→CO. H atoms are conducive to the activation of CO2, CO2+H→COOH→CO+OH is the dominant reaction pathway for CO2 activation. The first reaction in the whole system is the first C−H bond cleavage of ethane.

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“…This type of plots is useful to analyze the non-covalent interactions within the system under study. [21,32] In Figure 4, the NCI plots of TS4anti/reB and TS4syn/siB are presented, we can observe similar interactions in both TSs.…”

Section: Resultsmentioning

confidence: 56%

Mechanistic Study on the Asymmetric Synthesis of the Wieland‐Miescher Ketone and Analogs

et al. 2019

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The organocatalyzed synthesis of the Wieland‐Miescher ketone (WMK) via N‐sulfonyl‐binamprolinamide catalysis was investigated using experimental and computational tools. A mechanistic proposal is presented describing the origin of the high enantioselectivity, which rivals that of aldolases. The computational study reveals that the role of the prolinamide catalyst is to lower the reaction barrier and determine the stereoselectivity of the product achieved, while the role of the carboxylic acid is to facilitate proton transfer steps. The effect of the acid co‐catalyst was confirmed by experiments. The role of the structure of the BINAM backbone and the effect of the sulfonamide group are uncovered experimentally and computationally. Calculations show that a rigid highly defined catalytic pocket due to covalent and steric interactions induces conformational changes in the triketone substrate to maximize interactions.

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Insights into the N-Heterocyclic Carbene (NHC)-Catalyzed Oxidative γ-C(sp³)–H Deprotonation of Alkylenals and Cascade [4 + 2] Cycloaddition with Alkenylisoxazoles

Cited by 62 publications

References 105 publications

Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Activation Pathway of C‐H and C–C Bonds of Ethane by Pd Atom with CO₂ as a Soft Oxidant

Mechanistic Study on the Asymmetric Synthesis of the Wieland‐Miescher Ketone and Analogs

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Insights into the N-Heterocyclic Carbene (NHC)-Catalyzed Oxidative γ-C(sp3)–H Deprotonation of Alkylenals and Cascade [4 + 2] Cycloaddition with Alkenylisoxazoles

Cited by 62 publications

References 105 publications

Reaction Mechanism and Kinetics study on Addition of CCl4 to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Reaction Mechanism and Kinetics study on Addition of CCl4 to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Activation Pathway of C‐H and C–C Bonds of Ethane by Pd Atom with CO2 as a Soft Oxidant

Mechanistic Study on the Asymmetric Synthesis of the Wieland‐Miescher Ketone and Analogs

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Insights into the N-Heterocyclic Carbene (NHC)-Catalyzed Oxidative γ-C(sp³)–H Deprotonation of Alkylenals and Cascade [4 + 2] Cycloaddition with Alkenylisoxazoles

Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Reaction Mechanism and Kinetics study on Addition of CCl₄ to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond

Activation Pathway of C‐H and C–C Bonds of Ethane by Pd Atom with CO₂ as a Soft Oxidant