JOURNAL OF ORGANIC CHEMISTRY
·
2021
·
IF 4.354
Yan-Ling Song,Bei Li,Zhen-Biao Xie,Dan Wang,Hong-Mei Sun
Iron-catalyzed oxidative amination of benzylic C(sp3)–H bonds with anilines bearing electron-withdrawing groups (EWGs) or electron-donating groups (EDGs) is realized based on simple variations of N-substituents on imidazolium cations in novel ionic Fe(III) complexes. The structural modification of the imidazolium cation resulted in regulation of the redox potential and the catalytic performance of the iron metal center. Using DTBP as oxidant, [HItBu][FeBr4] showed the highest catalytic activity for anilines bearing EWGs, while [HIPym][FeBr4] was more efficient for EDG-substituted anilines. This work provides alternative access to benzylamines with the advantages of both a wide substrate scope and iron catalysis.
研究领域:
有机化学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Molecular Catalysis
·
2024
·
IF 3.9
Guiyu Chen,Wei Liu,Shiqiang Wang,Yongxiang Miao,Zhibin Song
Quinazolinone-based boron difluoride (BF 2 ) complexes were developed for the synthesis of dihydroisoquinolones, 2-phenylisoindolinone, 1-isochromanone and diarylketone through α-C(sp 3 )-H photooxidation. Seven selected quinazolinone-based BF 2 complexes exhibited good activity for photooxidation reaction using air as oxidant. It is worth noting that quinazolinone-based BF 2 as photocatalysts do not require the introduction of halogen heavy atoms to improve catalytic activity. Mechanism exploration indicated these BF 2 catalysts may involve a single electron transfer (SET) mediated photoredox catalysis to achieve α-C(sp3)-H oxidation. These quinazolinone-based BF 2 catalysts with facile preparation and structural modifiability would be good choice for organic oxidative transformation in the future.
研究领域:
有机化学
·
光化学
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULES
·
2020
·
IF 5.918
Jia Wang,Yue Chen,Canbin Ye,Anjun Qin,Ben Zhong Tang
The heteroatom-containing polymers are important components of advanced functional materials. Among the tremendous synthetic methodologies, polymerization via C–H activation is a powerful tool for the preparation of functional heteroatom-containing polymers, which should be further enriched, especially via C(sp3)–H activation. In this work, a new atom economic Pd(0)/benzoic acid catalyzed polymerization of internal diynes and secondary diamines via C(sp3)–H activation; i.e., C(sp3)–H polyamination of internal alkynes was successfully established. A series of regio- and stereoregular functional poly(allylic tertiary amine)s with high weight-average molecular weights (Mw, up to 25 600) were synthesized in excellent yields (up to 98%). The resultant polymers possess good solubility and film-forming ability, and their thin films exhibit high refraction indices (RI) with the range of 1.7207–1.6797 at 632.8 nm. Moreover, all the poly(allylic tertiary amine)s are emissive in solution and solid states. Thanks to the tolerance to functional groups of this polymerization, the tetraphenylethene (TPE) moiety could be facilely incorporated to endow the resultant polymers with the unique aggregation-enhanced emission (AEE) characteristics. Thus, this work not only establishes a powerful C(sp3)–H polyamination but also provides a strategy to facilely prepare functional nitrogen-containing acetylenic polymers.
研究领域:
有机化学
·
高分子化学
·
材料科学
✓ 已验证
DOI
高影响因子
ACS Omega
·
2020
·
IF 2.87
Zhenghong Zhou,Kangfei Hu,Jiawei Wang,Zhibin Li,Yan Zhang,Zhenggen Zha,Zhiyong Wang
An electrochemical synthesis for quinazolines and quinazolinones was developed via a C(sp3)-H amination/C-N cleavage by virtue of the anodic oxidation. The reaction can be carried out in aqueous media under mild conditions to afford the desired products with high yields. The reaction mechanism was proposed after detailed investigation.
研究领域:
有机化学
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2024
·
IF 3.3
Jun-Feng Yang,Yun-Fei Liu,Lin-Lin Wei,Kai-Kai Qiao,Yan-Qiu Zhao,Lei Shi
The Minisci-type dehydrogenative coupling of N-heteroaromatic rings with inert C–H or Si–H partners via visible-light-catalyzed hydrogen atom transfer has been reported. This methodology allows the coupling reactions to be carried out in water as a solvent under air atmospheric conditions with visible-light illumination. A wide range of inert C–H and Si–H partners could be directly coupled with various N-aromatic heterocycles to deliver products in good to excellent yields.
研究领域:
有机化学
·
光化学
✓ 已验证
DOI
PubMed
高影响因子
Solar RRL
·
2021
·Vol. 5
·期 12
·2100559
·
IF 8.582
Hong-Hong Zhang,Zi-Chun Zhou,Yu-Jie Dong,Li Zhang,Hong-Yan Chen,Dai-Bin Kuang
Utilizing halide perovskites for photocatalytic aromatic C( sp 3 ) H bond activation remains a great challenge due to the serious recombination of photogenerated charge carriers and slow reaction dynamics of the materials themselves. Herein, a lead-free perovskite-based hybrid of Cs 3 Sb 2 Br 9 /g-C 3 N 4 nanosheet is constructed and applied for photocatalytic aromatic C( sp 3 ) H bond activation, which shows enhanced photocatalytic performance. By introducing ultrathin g-C 3 N 4 nanosheets as the heterogeneous nucleation sites, size-reduced and well-dispersed Cs 3 Sb 2 Br 9 nanocrystals can be obtained. The as-formed close contact and high-quality heterointerface between Cs 3 Sb 2 Br 9 and g-C 3 N 4 provides pathways for fast charge transfer which is beneficial to improve the separation efficiency of photogenerated electron−hole pairs. Under visible light irradiation, the Cs 3 Sb 2 Br 9 /g-C 3 N 4 hybrid photocatalyst can effectively oxidize toluene toward benzaldehyde and benzyl alcohol with a total conversion rate of 8346.8 μmol g −1 h −1 , which is 26.6- and 6.0-fold that of pure g-C 3 N 4 and Cs 3 Sb 2 Br 9 , respectively. This work demonstrates the potential of all-inorganic lead-free halide perovskite-based heterostructures for photocatalytic organic reactions.
研究领域:
材料科学
·
化学
·
光催化
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Yu-Yang Liu,Shan Xu,Xiao-Xin Li,Run-Han Li,Xin-Ting Cai,Hui-Zhen Zhong,Jiang Liu,Qing Huang,Lei Zhang,Shun-Li Li,Ya-Qian Lan
Developing strategies and photocatalysts for C(sp3)-H bond functionalization under simple and mild conditions is important but challenging. Here, we report two redox heterocluster-based frameworks, named Ni5-PW12 and Ni5-V16, in which the terminal oxygen atoms of polyoxometalates are directly coordinated to metal atoms in metal–organic clusters. Due to the coexisting strong oxidation and reduction capacities, both of these photocatalysts achieve photocatalytic C(sp3)-H bond oxidative imination through combining oxidation of methyl aromatics and reduction of nitro aromatics reactions. The experimental and theoretical results reveal that benefiting from the short distance between the clusters, the rapid charge transfer and mass transfer processes would enhance the photocatalytic reactivity and inhibit side reactions. More importantly, all of the photocatalytic reactions are carried out in mild conditions at room temperature without any additional solvents, photosensitizers, oxidizing or reducing agents, or cocatalysts.
研究领域:
光催化
·
有机合成
·
材料化学
·
簇化学
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULAR CHEMISTRY AND PHYSICS
·
2023
·Vol. 224
·期 23
·2300304
·
IF 2.5
Mingzhao Li,Jia Wang,Anjun Qin,Ben Zhong Tang
Hyperbranched polymers have been widely applied in various fields because of their good solubility, high reactive end groups, and low viscosity, etc. Therefore, it is of great importance to develop new strategies to build multifunctional hyperbranched polymers with novel architectures. In this work, a C(sp 3 )─H activation-based polymerization of internal alkynes and bifunctional secondary amines is successfully established, and multifunctional hyperbranched polyamines (hb-PAs) with 100% E -isomers and high molecular weights ( M w up to 76 500) are prepared in good yields (up to 82%). The hb-PAs containing tetraphenylethylene moiety show unique aggregation-enhanced emission properties and can be used for explosive detection with a low limit of detection (9.14 × 10 −8 m ). Notably, the hb-PAs display high refractive indices (up to 1.7607) that can be further modulated to 1.7825 by the coordination of its peripheral ethynyl group with metallic cobalt. Moreover, the hyperbranched structure endows the hb-PAs with much better properties than their linear counterparts, such as higher photoluminescence quantum yields and refractive indices. In addition, the hb-PAs can be modified by a C(sp 3 )─H activation reaction of internal alkynes and alcohols. This work not only prepares a series of functional nitrogen-containing hyperbranched polymers but also promotes the application of C(sp 3 )─H activation in polymer chemistry.
研究领域:
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2010
·
IF 5.288
Hengquan Yang,Guang Li,Zhancheng Ma,Jianbin Chao,Zhiqiang Guo
New cubic cage-like mesoporous materials with a bulky N-heterocyclic carbene [IPr, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] precursor in the framework were synthesized by a co-condensation of IPr precursor-bridged organosilane and TEOS in the presence of template. N 2 sorption, XRD and TEM characterizations revealed that the mesostructural orderings of the synthesized materials depended on the molar fraction of the bridged organosilane in the initial gel mixture. With the increase in the molar fraction of the organosilane from 2.5% to 15%, the mesostructure of the synthesized material changed from a well-ordered 3D ordered structure to a amorphous structure. FT-IR and solid-state NMR characterizations confirmed that IPr carbene precursor was covalently integrated with the solid materials. Such hybrid materials were able to coordinate Pd(acac) 2 , leading to active solid catalysts for Suzuki–Miyaura couplings of less reactive aryl chlorides. The solid catalyst could be reused 8 times without a significant decrease in activity. Furthermore, the solid catalyst was active for the coupling of C(sp 3 )-chlorides and arylboronic acids.
研究领域:
材料化学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2023
·
IF 3.6
Shuo Li,Xian Xu,Qianlin Sun,Xin Xu
This work reports an intramolecular C(sp3)–H annulation of functionalized 2,6-lutidines catalyzed by an organocalcium hydride [{(DIPPnacnac)CaH(thf)}2] (DIPPnacnac = CH{(CMe)(2,6-iPr2–C6H3N)}2). This reaction constitutes a streamlined approach for producing a new family of tetrahydro-1,5-naphthyridines and hexahydropyrido[3,2-b]azocines derivatives in good to excellent yields with high atom efficiency and broad substrates scope. A calcium alkyl complex was isolated from the stoichiometric reaction between calcium hydride and the substrate through deprotonation, which was structurally characterized and confirmed as the catalytic intermediate.
研究领域:
有机化学
·
催化
·
合成化学
✓ 已验证
DOI
高影响因子
GREEN CHEMISTRY
·
2021
·Vol. 24
·期 1
·384-393
·
IF 10.182
Qi Zhang,Shouxin Liu,Xia Tian,Yidong Liu,Shiming Fan,Baibiao Huang,Andrew Whiting
A highly selective, green and sustainable chlorination of aliphatic C–H bonds is reported using MCln under the co-catalysis of visible light and nano-Cu@CuCl, which was synthesised via a one-step, hydrothermal strategy using copper(II) sulfate and D-glucose as the reducing agent in a KCl solution. A novel cascade method of producing Cl2 occurs in situ chlorinating C(sp3)–Hs, achieved through nano-Cu@CuCl catalysis using inorganic chloride MCln as a chlorine source under visible light and without the need for a strong oxidant. The reaction was applied to the chlorination of different alkylarene α-Hs and cyclic hydrocarbons C–HS and was developed for use in a photocatalytic serial reactor system which accomplished the chlorination of toluene α-Hs to give 92% conversion, 90% yield and 98% selectivity. Electron spin resonance (ESR) studies of DMPO-Cl. revealed that the reaction mechanism belonged to a free radical process.
研究领域:
有机化学
·
绿色化学
·
材料科学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Tao Shan,Sunzai Ke,Xin Yang,Xuhui Yang,Bo Weng,Lijuan Shen,Min-Quan Yang
Photocatalytic selective oxidation of aromatic hydrocarbons plays an important role in the production of value-added chemicals. A key step in this process is the activation of C(sp 3 )-H bond by photogenerated holes. However, the inadequate hole generation and lack of surface adsorption-activation sites severely hinders the improvement in photocatalytic C-H bond oxidation. In particular, the random charge migration to the surface impedes the effective capture of holes by surface active sites to dissociate the C(sp 3 )-H bond. Here, we design and fabricate a Co 3 O 4 /Cs 3 Sb 2 Br 9 p-n heterojunction that effectively addresses these challenges. The p-n heterojunction forms strong built-in electric fields (BEF) facilitating spatial charge separation. Holes are accumulated on Co 3 O 4 , while electrons are accumulated on Cs 3 Sb 2 Br 9 , thereby offering abundant active holes and electrons. Moreover, Co 3 O 4 shows stronger adsorption and activation capacity for the C(sp³)-H bond, enabling the C(sp 3 )-H bond dissociation with low reaction energy barrier. Consequently, the holes are directionally extracted from photoactive Cs 3 Sb 2 Br 9 to catalytically active Co 3 O 4 under visible light irradiation, thereby accelerating the toluene oxidation. The optimized 5 % Co 3 O 4 /Cs 3 Sb 2 Br 9 exhibits a benzyl aldehyde (BAD) evolution rate of 5044 μmol g −1 h −1 and a benzyl alcohol (BA) production rate of 1820 μmol g −1 h −1 , which are 12 and 17 times higher than that of blank Cs 3 Sb 2 Br 9 , respectively.
研究领域:
材料科学
·
化学工程
·
光化学
·
催化
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）