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SYNTHETIC COMMUNICATIONS · 2018 · IF 1.377

Pd-catalyzed regioselective C-H chlorination of disubstituted 1,2,3-triazoles

Xinyuan Ma,Qiong Mo,Jie Chang,Kai Xie

This paper mainly studied Pd-catalyzed regioselective chlorination of disubstituted 1,2,3-triazoles directed by the 1,2,3-triazole ring. A series of regioselective chlorinated products were synthesized in 47–86% yields using Pd(OAc)2 as a catalyst and CuCl2 as a chlorinated reagent. This method provides a new mean for the synthesis of 1,2,3-triazole halides which combines the formation of C-X bond with C-H activation.

研究领域: 有机化学 · 合成化学
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Polymer Chemistry · 2022 ·Vol. 13 ·期 10 ·1437-1445 · IF 5.364

A multi-functional chromone-modified polyethylene obtained by metal-free C–H activation

Yongjie Zhang,Xiaopei Li,Wenqin Zhu,Pibo Liu,Juntao Ren,Shangtao Chen,Yanming Hu,Guangyuan Zhou

Post-modification of polyolefins by cutting-edge C–H activation has recently emerged as an attractive methodology for the incorporation of precise functionalities, thus expanding their applicability and creating value-added materials. In this report, chromone (CM), the core of naturally occurring molecules possessing manifold biological and pharmacological activities, was incorporated into polyethylene (PE) through the recently developed radical-mediated alkane C–H activation approach. The reaction was conducted in the presence of di-tertbutyl peroxide as the oxidant and a small amount of naphthalene as the solvent or under solvent-free conditions. The produced CM-grafted PEs (CM-PEs) exhibited intriguing antioxidative and fluorescence properties as revealed by thermogravimetric analysis (TGA) and fluorescence microscopy. Moreover, CM-PEs were successfully demonstrated to act as a polymer-bound antioxidant, a fluorescence marker for plastic sorting, and a traceable compatibilizer for the PE/polystyrene blend, revealing that CM-PE is a multi-functional material.

CAS / MDL: 491-38-3
研究领域: 材料科学 · 高分子化学 · 生物医学工程
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EUROPEAN JOURNAL OF ORGANIC CHEMISTRY · 2022 ·Vol. 2022 ·期 33 ·e202200316 · IF 3.261

Quinazoline-Assisted ortho-Halogenation with N-Halosuccinimides through Pd(II)-Catalyzed C(sp2)−H Activation

Yong Wang,Hui Wang,Qifan Yang,Shihua Xie,Hongjun Zhu

Graphical Herein, palladium(II)-catalyzed halogenation of 2-phenylquinazolines using N -halosuccinimides as halogen sources was described via C−H activation under mild reaction conditions. A series of halogen-substituted 2-arylquinazolines were synthesized through C−H functionalization. An efficient quinazoline-assisted ortho -halogenation of 2-arylquinazolines has been developed using N -halosuccinimides as halogen sources with Pd(II)-catalyzed C−H bond activation. No additional ligand and oxidant are required. This protocol is highly regioselective and applicable to a broad range of quinazoline substrates bearing different functional groups, giving yields of up to 98 %. The mechanism of the quinazoline ortho -halogenation was investigated by comprehensive experimentation.

研究领域: 有机化学 · 合成化学
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JOURNAL OF ORGANIC CHEMISTRY · 2022 · IF 4.198

Rh(III)-Catalyzed One-Pot Three-Component Diannulation of Benzils, Ammonium Acetate, and Alkynes to Build 1,1′-Biisoquinolines

Shihai Lv,Ya-Nan Tian,Yanyan Yang,Chaoying Wen,Shiqing Li

An efficient one-pot synthesis of 1,1′-biisoquinolines by a three-component reaction of commercially available raw materials (benzils, NH4OAc, and alkynes) is disclosed. This complicated reaction involves in situ diimine formation via benzil-NH4OAc condensation, Rh(III)-catalyzed 2-fold imine-directed C–H activation, and annulation with alkynes. Both symmetric and unsymmetric 1,1′-biisoquinolines could be assembled in moderate to high yields. The reaction mechanism is supported through ESI-MS, in which Cp*ClRh+, Cp*(OAc)Rh+, Cp*(OPiv)Rh+, and two rhodacycle intermediates are successfully detected to explain the evolution of rhodium species.

研究领域: 有机化学 · 合成化学
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JOURNAL OF ORGANIC CHEMISTRY · 2018 · IF 4.805

Mixing O-Containing and N-Containing Directing Groups for C–H Activation: A Strategy for the Synthesis of Highly Functionalized 2,2′-Biaryls

Chao Zhang,Yugang Song,Zhihui Sang,Lingpeng Zhan,Yu Rao

A strategy combining O- and N-containing directing groups has been developed for the synthesis of 2,2′-biaryl via Pd-mediated C–H bond activation and oxidative coupling. This new transformation may proceed through a mechanism involving Pd(II) and Pd(IV) intermediates. We found the use of PTSA and HFIP to be critical for the reaction and suggest that these reagents could serve as efficient ligands for this C–C bond formation. This methodology provides broad functional group tolerance, excellent reactivity, and high yields.

研究领域: 有机化学 · 合成化学
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JOURNAL OF ORGANIC CHEMISTRY · 2023 · IF 3.6

Multideuteration of Nitroaromatics by Silver-Catalyzed Hydrogen-Isotope Exchange

Jianbo Tang,Junhua Kong,Hui Xu,Zhi-Jiang Jiang,Yifan She,Jianfei Bai,Bencan Tang,Jia Chen,Zhanghua Gao,Kun Gao

Silver-catalyzed deuteration of nitroaromatics has been achieved using D2O as the deuterium source. Distinct from the well-established directing group-guided hydrogen-isotope exchange, this protocol showed an interesting deuteration pattern, where considerable deuterium accumulation was observed around the aromatic rings. Controlling experiments suggested that the deuteration was initiated by a silver-promoted C–H activation. Therefore, a tentative two-stage deuteration mechanism involving aryl-silver species was proposed to explain the deuteration on meta- and para-positions.

研究领域: 有机化学 · 同位素化学
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SYNLETT · 2025 · IF 1.4

Ligand Promoted PdII-Catalyzed Ortho-Hydroxylation of Masked Benzyl Alcohols

Ke-Yang Huang,Ze-Yu Wu,Jun Luo,Chao Jiang

A PdII-catalyzed ortho-C(sp²)−H hydroxylation of benzyl alcohols using oxime ether as a monodentate directing group was developed. The N-acetyl glycine ligand is crucial to the reactivity through facilitating the C−H cleavage. The reaction might involve the formation of hydroxyl radicals generated from oxone and a 6-membered exo-palladacycle intermediate was proposed. Various substituents on the phenyl ring were tolerated in the reaction. Gram-scale reaction and directing group removal were also demonstrated to show its applicability for the syntheses of salicyl alcohols.

CAS / MDL: 70693-62-8
研究领域: 有机化学 · 合成化学
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APPLIED ORGANOMETALLIC CHEMISTRY · 2014 ·Vol. 28 ·期 9 ·673-677 · IF 2.017

Chemoselective one-pot synthesis of terphenyl derivatives by sequential directed C―H functionalization–Suzuki coupling

Limin Ren,Wenyi Chu,Dinghui Guan,Yanjun Hou,Man Wang,Xiaobin Yuan,Zhizhong Sun

A simple and efficient route for the preparation of terphenyl derivatives via palladium-catalyzed sequential directed C―H arylation/Suzuki–Miyaura cross-coupling in ‘one-pot’ has been developed. 4,4′-(Cyclohexane-1,1-diyl)diphenol is an essential ligand. This reaction can tolerate a series of functional groups and provides the terphenyl derivatives in moderate to good yield. Copyright © 2014 John Wiley & Sons, Ltd.

研究领域: 有机化学 · 合成化学
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Asian Journal of Organic Chemistry · 2017 ·Vol. 7 ·期 1 ·240-247 · IF 2.788

Rhodium-Catalyzed Alkenyl C−H Activation and Oxidative Coupling with Allylic Alcohols

Rui Yan,Zhong-Xia Wang

Graphical Oxidative coupling of allylic alcohols : [Cp*RhCl 2 ] 2 was demonstrated to catalyze the oxidative coupling of alkenylpyridines with allylic alcohols through alkenyl C−H activation in the presence of AgOTf and AgOAc to afford β-alkenyl ketones and aldehydes in moderate to good yields. [Cp*RhCl 2 ] 2 was demonstrated to catalyze the oxidative coupling of alkenylpyridines with allylic alcohols through alkenyl C−H activation in the presence of AgOTf and AgOAc to afford β-alkenyl ketones and aldehydes in moderate to good yields. Allylic alcohol, 1-aryl and 1-alkyl allylic alcohols can be coupled with various alkenylpyridines. The reaction occurred at the γ-position of allylic alcohols and the cis -β-position of the alkenylpyridines.

研究领域: 有机化学 · 催化化学
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ENERGY & FUELS · 2022 · IF 4.654

Imidazole-Dependent Assembly of Copper Polymolybdate Frameworks for One-Pot Sulfide Oxidation and C–H Activation

Xianqiang Huang,Yanan Cui,Gang Liu,Haitao Wang,Junyu Ren,Yalin Zhang,Guodong Shen,Lingling Lv,Huai-Wei Wang,Yi-Fa Chen

With the arising concern of environmental problems, the removal of polycyclic aromatic hydrocarbons or sulfides in fuel oils is an indispensable process to achieve a clean energy source. At present, direct catalytic oxidation of benzyl C–H bonds of polycyclic aromatic hydrocarbons and sulfides to corresponding carbonyl compounds is very attractive, yet their simultaneous oxidation using a single economical-friendly catalyst is not yet well established. Here, three imidazole-decorated copper polyoxomolybdate frameworks (Im-Cu-PMoFs) are successfully synthesized by tuning different imidazole derivatives. These Im-Cu-PMoFs can serve as effective heterogeneous catalysts for the one-pot oxidation of benzylic hydrocarbons and sulfides to produce carbonyl compounds. Specifically, Im-Cu-PMoFs-3 as a single component catalyst exhibits high activity and prominent selectivity (conversion up to 99% and selectivity up to 99%) in the one-pot reaction. In addition, the possible reaction pathway and active sites are supported by sufficient characterizations and DFT calculations, which reveal the synergistic effect of Mo(VI) and Cu(II) centers in the one-pot catalysis reaction. These dual function-validated frameworks hold much promise in the exploration of novel catalysts for applications like continuous catalytic or flow bed reaction.

CAS / MDL: 71-43-2
研究领域: 化学 · 环境科学 · 材料科学
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iScience · 2022 · IF 6.107

Unlocking a self-catalytic cycle in a copper-catalyzed aerobic oxidative coupling/cyclization reaction

Jianming Liu,Xiaopei Wang,Zhiyue Wang,Yan Yang,Qinghu Tang,Hongchi Liu,Hanmin Huang

Summary Presented here is a copper-catalyzed, aerobic oxidative C-H/C-H cyclization reaction, which occurs by cleaving the C-H and N-H bonds of 3-phenylindoles. A broad range of 3-phenylindoles can be well tolerated to produce the indole-containing polycyclic aromatic hydrocarbons (PAH) in good to excellent yields. An evaluation of the reaction mechanism is enabled by the isolation of the di- and tri-indole intermediates, highlighting the role of the substrate for this catalytic reaction. The results of these controlled experiments and kinetic studies provide solid experimental support for a self-catalysis reaction, which has rarely been observed in oxidative C-H activation reactions. Additional mechanistic studies indicate that the substrate for this reaction accelerates by the following mechanism: The substrate combines with the Cu catalyst to transform the less active di-indole intermediate into a tri-indole intermediate. This intermediate is quickly converted into the desired product along with regeneration of the substrate copper complex.

研究领域: 有机化学 · 催化化学
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FUEL · 2023 · IF 7.4

Highly dispersed and stable NiSn subnanoclusters encapsulated within Silicalite-1 zeolite for efficient propane dehydrogenation

Meiyu Liu,Xinyu Sun,Yiming Zhang,Ye Yang,Yucai Qin,Binbin He,Yi Mei,Yun Zu

Propane dehydrogenation (PDH) is one of the most effective methods for intentional (“on-purpose”) propylene production. Isolated Sn sites on open supports exhibit considerable PDH performance comparable to that of industrial Pt- and Cr-based catalysts, but the loss of Sn is inevitable. Herein, highly dispersed and stable NiSn subnanoclusters encapsulated within the channels of silicalite-1 zeolite are fabricated through a one-step hydrothermal synthesis in this work. The as-prepared Ni 1 Sn 1 @S-1 zeolite catalyst exhibits outstanding PDH performance with considerable propylene formation rate (ca. 12.3 mmol∙g cat -1 ∙h −1 ) and high propylene selectivity (>88 %). Most significantly, no Sn loss is detected after three regeneration cycles. Structural elucidation of NiSn sites on catalysts, by HRTEM, H 2 -TPR, FTIR and XPS characterizations confirms that the Ni sites embedded in the geminal silanols of zeolitic framework play a vital role in anchoring Sn species and preventing the active sites from losing and sintering. The cooperative action of robust NiSn subnanoclusters is conducive to the selective C–H activation and the propylene desorption. A plausible dehydrogenation mechanism is revealed by in situ infrared spectroscopy. This study on siliceous zeolite confined NiSn catalysts delivers an insight into the nature of selective and stable NiSn sites involved in the PDH reaction.

研究领域: 催化化学 · 材料科学
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