Rhodium-Catalyzed Azine-Directed C–H Amidation with <i>N</i>-Methoxyamides

Ban, Tao; Vu, Huu-Manh; Zhang, Jing; Yong, Jia-Yuan; Liu, Qiong; Li, Xuqin

doi:10.1021/acs.joc.1c02868

Cited by 6 publications

(2 citation statements)

References 53 publications

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“…[4] But anatase TiO 2 in the form of octahedral coordination is harmful because it could decompose H 2 O 2 and then reduce the effective utilization of oxidants. [21][22][23] However, Ti species are likely to aggregate and generate anatase owing to the mismatched hydrolysis rate of Ti source and Si source. [24] Furthermore, the crossed micropore channel of TS-1 less than 2 nm limits the accessibility of bulky molecules to active sites, [2,10,25] resulting in the low conversion of substrates.…”

Section: Introductionmentioning

confidence: 99%

Aromatic compounds‐mediated synthesis of anatase‐free hierarchical TS‐1 zeolite: Exploring design strategies via machine learning and enhanced catalytic performance

Wang

Lin

et al. 2023

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Simultaneous achievement of constructing mesopores and eliminating anatase is a long‐term pursuit for enhancing the catalytic performance of TS‐1. Here, we developed an aromatic compounds‐mediated synthesis method to prepare anatase‐free and hierarchical TS‐1 for olefin epoxidation. A series of hierarchical TS‐1 zeolites were prepared by introducing aromatic compounds containing different functional groups via the crystallization process. The formation of intercrystalline mesopores and insertion of titanium into framework were facilitated at different extent. The synergistic coordination of carboxyl and hydroxyl in aromatic compounds with Ti(OH)4 realizes the uniform distribution of titanium species and eliminates the generation of anatase. Noteworthily, eight machine learning models were trained to reveal the mechanism of additive functional groups and preparation conditions on anatase formation and microstructure optimization. The prediction accuracy of most models can reach more than 80%. Benefiting from the larger mesopore volumes (0.37 cm3·g−1) and higher content of framework Ti species, TS‐DHBDC‐48h samples exhibit a higher catalytic performance than other zeolites, giving 1‐hexene conversion of 49.3% and 1,2‐epoxyhenane selectivity of 99.9%. The paper provides a facile aromatic compounds‐mediated synthesis strategy and promotes the application of machine learning toward the design and optimization of new zeolites.

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Section: Introductionmentioning

confidence: 99%

Aromatic compounds‐mediated synthesis of anatase‐free hierarchical TS‐1 zeolite: Exploring design strategies via machine learning and enhanced catalytic performance

Wang

Lin

et al. 2023

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“…The carbon–nitrogen bonds are present in many of the most privileged structures found in both natural products and synthetic bioactive molecules, which play a pivotal role in medicinal chemistry, pharmaceutical science, and functional materials. − Hence, the approaches to create the C–N bonds have been studied in the past decades. Among these well-constructed routes, transition metal-catalyzed C–H amidation is an efficient, direct, and classic method to access C–N bonds. − Many transition metals, such as Mn, , Fe, , Co, − Ni, , Cu, , Ru, − Rh, − Pd, , and Ir, ,− have been employed in the C–H amidation.…”

Section: Introductionmentioning

confidence: 99%

Comprehensive Theoretical Study of Cp*Ir^III-Catalyzed Intermolecular Enantioselective Allylic C–H Amidation: Reaction Mechanism, Electronic Processes, and Regioselectivity

2023

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Density functional theory was used to elucidate the reaction mechanism of Cp*IrIII-catalyzed intermolecular regioselective C(sp3)–H amidation of alkenes with methyl dioxazolones. All substrates, intermediates, and transition states were fully optimized at the ωB97XD/6-31G(d,p) level (LANL2DZ(f) for Ir). The computational results revealed that this amidation occurred through the IrIII/IrV catalytic cycle, involving four important elementary steps: C–H bond activation, oxidative addition of methyl dioxazolone, reductive elimination, and proto-demetalation, and the first was the rate-determining step. The C–H bond activation showed good α- and branch-regioselectivity, decided by the distortion energy of 2-pentene and the interaction energy of the transition state, respectively. The oxidative addition of dioxazolone occurred in one elementary step with CO2 disassociation. The reductive elimination showed good branch-regioselectivity determined by the distorted energy of the allyl group. In the proto-demetalation, hydrogen directly transferred from the oxygen atom to the nitrogen atom. Moreover, to clarify the effect of the substituted groups, selected 12 substrates were also discussed in this text.

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Well Defined Phosphine Free Ni‐Catalyzed Dehydrogenation of Secondary Alcohols for the Synthesis of Ketones and Ketazines

Maji,

Singh,

Sharma

et al. 2024

Chemistry An Asian Journal

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In this work, we unveil a novel synthesis of bench stable Ni (II) complexes supported by tetradentate Schiff‐base ligands and the complexes were devoid of any phosphine or phosphine‐based ligand. These Ni‐complexes were successfully applied for the dehydrogenation of secondary alcohols for ketone and ketazine syntheses. Secondary alcohols with different functional groups were well tolerated during catalytic cycle. Moreover, we successfully extended this protocol for the synthesis of biologically significant ketones and ketazines. On the basis of various control experiments, probable reaction pathway was proposed and an acceptorless alcohol dehydrogenation mechanism was suggested.

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Rhodium-Catalyzed Azine-Directed C–H Amidation with N-Methoxyamides

Cited by 6 publications

References 53 publications

Aromatic compounds‐mediated synthesis of anatase‐free hierarchical TS‐1 zeolite: Exploring design strategies via machine learning and enhanced catalytic performance

Aromatic compounds‐mediated synthesis of anatase‐free hierarchical TS‐1 zeolite: Exploring design strategies via machine learning and enhanced catalytic performance

Comprehensive Theoretical Study of Cp*Ir^III-Catalyzed Intermolecular Enantioselective Allylic C–H Amidation: Reaction Mechanism, Electronic Processes, and Regioselectivity

Well Defined Phosphine Free Ni‐Catalyzed Dehydrogenation of Secondary Alcohols for the Synthesis of Ketones and Ketazines

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Rhodium-Catalyzed Azine-Directed C–H Amidation with N-Methoxyamides

Cited by 6 publications

References 53 publications

Aromatic compounds‐mediated synthesis of anatase‐free hierarchical TS‐1 zeolite: Exploring design strategies via machine learning and enhanced catalytic performance

Aromatic compounds‐mediated synthesis of anatase‐free hierarchical TS‐1 zeolite: Exploring design strategies via machine learning and enhanced catalytic performance

Comprehensive Theoretical Study of Cp*IrIII-Catalyzed Intermolecular Enantioselective Allylic C–H Amidation: Reaction Mechanism, Electronic Processes, and Regioselectivity

Well Defined Phosphine Free Ni‐Catalyzed Dehydrogenation of Secondary Alcohols for the Synthesis of Ketones and Ketazines

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Comprehensive Theoretical Study of Cp*Ir^III-Catalyzed Intermolecular Enantioselective Allylic C–H Amidation: Reaction Mechanism, Electronic Processes, and Regioselectivity