DFT Mechanistic Insights into Aldehyde Deformylations with Biomimetic Metal–Dioxygen Complexes: Distinct Mechanisms and Reaction Rules

Zhao, Ruihua; Zhang, Beibei; Liu, Zheyuan; Cheng, Gui‐Juan; Wang, Zhixiang

doi:10.1021/jacsau.2c00014

Cited by 11 publications

(9 citation statements)

References 87 publications

(194 reference statements)

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“…Quantum mechanical density functional theory (DFT) methods have found a wide range of applications, especially in the field of predicting the properties of nanomaterials 24 – 27 , separation and purification of chemicals 28 – 30 , prediction of the mechanism of reactions 31 , and so on. Recently, some important methods such as functionalization/doping and size-dependent were used to enhance or control the material properties.…”

Section: Introductionmentioning

confidence: 99%

Quantum DFT methods to explore the interaction of 1-Adamantylamine with pristine, and P, As, Al, and Ga doped BN nanotubes

Nemati‐Kande

Pourasadi

Aghababaei

et al. 2022

Sci Rep

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Nanostructures, nowadays, found growing applications in different scientific and industrial areas. Nano-coins, nanosheets, and nanotubes are used in medical applications as sensors or drug delivery substances. The aim of this study is to explore the adsorption of 1-Adamantylamine drug on the pristine armchair boron nitride nanotubes (BNNTs) with BNNT(5,5), BNNT(6,6), and BNNT(7,7) chirality along with the P, As, Al and Ga-doped BNNTs, using the quantum mechanical density functional methods. Considering the fact that dispersion effects are important in the case of weak Van der Waals interactions, computations have been done using B3LYP hybrid functional with the implementation of the D3(BJ) empirical dispersion correction methods. Quantum theory of atoms in molecules, natural bonding orbitals, and Kohn–Sham orbitals were used to investigate the nature and type of the adsorption process. The results showed that, while the adsorption of 1-Adamantylamine on the outer surface of pristine BNNT is physical in nature, doping can improve the ability of detracted BN to adsorb the drug through chemical bonds. Also, it was found that, by increasing the radius of the BNNT the adsorption energy was decreased. In conclusion, results of the present work suggest that, Ga doped nanotube, due the chemisorption, is not an ideal nanotube in drug delivery of 1-Adamantylamine drug, whereas, the other studied cases physiosorbed the drug, and may not have serious problem in release of the 1-Adamantylamine drug.

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Section: Introductionmentioning

confidence: 99%

Quantum DFT methods to explore the interaction of 1-Adamantylamine with pristine, and P, As, Al, and Ga doped BN nanotubes

Nemati‐Kande

Pourasadi

Aghababaei

et al. 2022

Sci Rep

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“…Although the further hydrogen abstraction of the Cu(II)–O • complex is expected to generate a Cu(II)-OH complex, the energy barriers of the above pathways for the generation of the Cu(II)-O • complex have already exceeded 33 kcal/mol, showing that this mechanism is less possible. Cheng et al reported the addition of Cu(II)-O-O • species to the formyl group of aldehydes, followed by 1,2-alkyl shift and hydrogen atom abstraction to produce Cu(II)–OH . However, at the beginning of the aminooxygenation reactions, there is no aldehyde for realizing such a pathway.…”

Section: Resultsmentioning

confidence: 99%

“…Cheng et al reported the addition of Cu(II)-O-O • species to the formyl group of aldehydes, followed by 1,2-alkyl shift and hydrogen atom abstraction to produce Cu(II)−OH. 23 However, at the beginning of the aminooxygenation reactions, there is no aldehyde for realizing such a pathway.…”

Section: In Situ Generation Of Active Cu(ii) Complexes From Lcuoacmentioning

confidence: 99%

“…For the mechanism of Cu-catalyzed aerobic dehydrogenative reactions, Maseras, Zhu, and Zhao reported the trifluoromethylation, homocoupling, and phosphorylation of C(sp)–H bonds, respectively, and Koley reported the arylation of amine N–H bonds (Scheme a). For the mechanism of Cu-catalyzed aerobic oxygenative reactions, Cui and Thiel reported the coupling of phenols and alkynes to hydroxyl-functionalized aryl ketones, Jiang, Yang, and Bi reported the C(CO)–Me bond cleavage to form aldehydes, carboxylic acids and ketones, and Cheng , and Wang reported the hydroxylation of allylic C–H bonds and the HC(O)–R bond cleavage to form ketones and formic acids (Scheme b). In this context, mechanistic studies addressing other types of Cu-catalyzed aerobic reactions are still desired.…”

Section: Introductionmentioning

confidence: 99%

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Computation Study on Copper-Catalyzed Aerobic Intramolecular Aminooxygenative C═C Bond Cleavage to Imides: Different Roles of Mononuclear and Dinuclear Copper Complexes

Liu

Chen

et al. 2023

ACS Catal.

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Cu-catalyzed aerobic reactions are a powerful protocol for the synthesis of value-added chemicals based on the ideal oxidant O2. Despite the long research history, the mechanistic studies clarifying the details of the whole catalytic cycle, where Cu-O2 complexes and their derivatives directly participate in the conversion of substrates, are limited, leaving the mechanisms of emerging aerobic reactions far from understanding. Herein, a computational study on the mechanism of Cu-catalyzed aerobic aminooxygenation of alkene-tethered amides to imides is reported. It is found that the Cu(I) precursor is not the active species but can generate two types of Cu(II) complexes LCu(OAc)OH and LCu(OAc)OOR to start the aminooxygenation through the successive formation of dinuclear Cu(III) oxo complex, dinuclear Cu(II) hydroxide complex, and hetero-dinuclear Cu(II)-Cu(I) complex, followed by alkylperoxo radical capture with Cu(I) species. LCu(OAc)OH catalyzes the aminooxygenation via a mononuclear mechanism, while LCu(OAc)OOR is an active intermediate therein. In the initial catalytic stage, LCu(OAc)OH transforms alkene-tethered amides to α-amidated aldehydes through N–H activation, amide isomerization, cyclization, alkyl radical release, alkyl radical capture by O2, alkylperoxo radical capture by in situ-generated Cu(I) species to LCu(OAc)OOR, acetate-assisted proton-coupled electron transfer (PCET), and concerted PCET/O–O bond cleavage. In the second catalytic stage for the generation of imides from α-amidated aldehydes, the previously proposed aldehyde Cα–H pathway is possible, but it is more likely to generate CO2 and H2 as the byproducts. Instead, a more feasible pathway involving C(O)–H activation to acyl radical, decarbonylation, and radical capture to LCu(OAc)OOR′ was discovered. The C(O)–H activation pathway generates CO and H2O as the byproducts and is consistent with the experimental observations. The concerted PCET/O–O bond cleavage steps generating α-amidated aldehydes and imides have close energy barriers and both can be the rate-determining steps. The presented outcome revised and expanded the knowledge of Cu-catalyzed aerobic conversion of CC bonds and amide N–H bonds, highlighting the different roles of mononuclear and dinuclear copper complexes in the aerobic reactions and the in situ generation of Cu(II) catalysts, respectively.

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“…Metal–dioxygen species such as metal–(hydro)peroxo [M–O 2 (H)] complexes have been invoked as important reactive intermediates for various oxidative reactions in biological systems. − For examples, numerous M–O 2 (H) complexes have been reported to conduct nucleophilic reactions, including aldehyde deformylation in biomimetic models. − Several M–O 2 (H) species have been documented to readily oxidize nitriles under mild conditions (Scheme ). − In a rhodium complex with tert -butyl isocyanide and triethylphosphine ligands, it was revealed that the rhodium(III)–hydroperoxo intermediate is responsible for the nitrile activation to afford a rhodium(III)–peroxyimidato species (step a) .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into Nitrile Activation by Cobalt(III)–Hydroperoxo Intermediates: The Influence of Ligand Basicity

Son,

Jeong,

Kim

et al. 2023

JACS Au

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The versatile applications of nitrile have led to the widespread use of nitrile activation in the synthesis of pharmacologically and industrially valuable compounds. We reported the activation of nitriles using mononuclear cobalt(III)–hydroperoxo complexes, [CoIII(Me3-TPADP)(O2H)(RCN)]2+ [R = Me (2) and Ph (2 Ph)], to form cobalt(III)–peroxyimidato complexes, [CoIII(Me3-TPADP)(R–C(NH)O2)]2+ [R = Me (3) and Ph (3 Ph)]. The independence of the rate on the nitrile concentration and the positive Hammett value of 3.2(2) indicated that the reactions occur via an intramolecular nucleophilic attack of the hydroperoxide ligand to the coordinated nitrile carbon atom. In contrast, the previously reported cobalt(III)–hydroperoxo complex, [CoIII(TBDAP)(O2H)(CH3CN)]2+ (2 TBDAP), exhibited the deficiency of reactivity toward nitrile. The comparison of pK a values and redox potentials of 2 and 2 TBDAP showed that Me3-TPADP had a stronger ligand field strength than that of TBDAP. The density functional theory calculations for 2 and 2 TBDAP support that the strengthened ligand field in 2 is mainly due to the replacement of two tert-butyl amine donors in TBDAP with methyl groups in Me3-TPADP, resulting in the compression of the Co–Nax bond lengths. These results provide mechanistic evidence of nitrile activation by the cobalt(III)–hydroperoxo complex and indicate that the basicity dependent on the ligand framework contributes to the ability of nitrile activation.

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DFT Mechanistic Insights into Aldehyde Deformylations with Biomimetic Metal–Dioxygen Complexes: Distinct Mechanisms and Reaction Rules

Cited by 11 publications

References 87 publications

Quantum DFT methods to explore the interaction of 1-Adamantylamine with pristine, and P, As, Al, and Ga doped BN nanotubes

Quantum DFT methods to explore the interaction of 1-Adamantylamine with pristine, and P, As, Al, and Ga doped BN nanotubes

Computation Study on Copper-Catalyzed Aerobic Intramolecular Aminooxygenative C═C Bond Cleavage to Imides: Different Roles of Mononuclear and Dinuclear Copper Complexes

Mechanistic Insights into Nitrile Activation by Cobalt(III)–Hydroperoxo Intermediates: The Influence of Ligand Basicity

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