4.6 Article

Phosphine Ligand-Free Ruthenium Complexes as Efficient Catalysts for the Synthesis of Quinolines and Pyridines by Acceptorless Dehydrogenative Coupling Reactions

期刊

CHEMCATCHEM
卷 11, 期 10, 页码 2500-2510

出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.201900435

关键词

Ru complexes; acceptorless dehydrogenative coupling reactions; quinolines; pyridines; bifunctional catalysts

资金

  1. National Natural Science Foundation of China [21771131, 21471108, 21773163]
  2. Natural Science Foundation of Jiangsu Province [BK20161276]
  3. Scientific and Technologic Infrastructure of Suzhou [SZS201708]

向作者/读者索取更多资源

A series of phosphine-free Ru(III)/Ru(II) complexes of NH functionalized N<^> N<^> N pincer ligands exhibit excellent activity for acceptorless dehydrogenative coupling (ADC) of secondary alcohols with 2-aminobenzyl or.-amino alcohols to quinolines and pyridines. Ru(III) complexes [LRuCl3] (L= 6-(3-R1,5-R2-1H-pyrazol-1-yl)-N-(pyridin-2-yl) pyridin-2-amine; 1a: R1 = R2 = H (L1); 1b: R1= R2= Me (L2); 1c: R1= H, R2= CF3 (L3); 1d: R1= H, R2= Ph (L4); 1bMe: L= 6-(3,5-dimethyl-1H-pyrazol-1-yl)-N-methyl-N-(pyridin- 2-yl) pyridin-2-amine (L2Me)) were obtained by refluxing RuCl3 center dot xH2O with the corresponding ligand in EtOH. Five Ru(II) complexes [LRu(DMSO-kS) Cl2] (2a: L= L1; 2b: L= L2; 2c: L= L3; 2d: L= L4; 2bMe: L= L2Me) were formed by reducing the corresponding Ru(III) complex in refluxing EtOH. The latter complexes could also be prepared directly by refluxing Ru (DMSO) 4Cl2 with the corresponding ligand in EtOH. These Ru(III) and Ru(II) complexes, especially 1b/2b, exhibited high catalytic efficiency and broad functional group tolerance in ADC reactions of secondary alcohols with 2-aminobenzyl or.-amino alcohols to quinolines and pyridines. A detail mechanistic study indicated the Ru(III) complex was reduced into the Ru(II) species, which is the active catalytic center for ADC via a Ru H/ N H bifunctional outer-sphere mechanism. This protocol provides a reliable, atom-economical and environmentally benign procedure for C N and C C bond formation.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.6
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

Article Engineering, Environmental

Tailorable carbon cloth electrodes covered with heterostructured Co/CoO/ CoN interfaces for scalable electrocatalytic overall water splitting

Wei Zhang, Cong Li, Jun-Yang Ji, Zheng Niu, Hongwei Gu, Brendan F. Abrahams, Jian-Ping Lang

Summary: In this study, a Co/CoO/CoN heterostructure catalyst dispersed in hierarchical porous N-doped graphitic carbon on carbon cloth was prepared using a facile method. The active centers in the catalytic process were investigated by DFT calculations. Due to the strong interaction and electronic structure reconfiguration between interfaces, the optimized catalyst, Co/CoO/CoN/CC-2, exhibited remarkable catalytic activity for both HER and OER.

CHEMICAL ENGINEERING JOURNAL (2023)

Article Chemistry, Inorganic & Nuclear

A Cd-based MOF crystal vessel for the synthesis of interhalogens

Min-Jie Zhang, Yu Ge, Chen Cao, Xin-Ran Xue, Qiu-Yi Li, Qi Liu, Jian-Ping Lang

Summary: A flexible metal-organic framework (MOF), {[Cd(1,4-bdc)(4-bpa)]center dot DMF}n (1), was prepared and used to synthesize and store pure interhalogens. The embedded interhalogen molecules were stabilized by interactions with the inner groups of the porous framework and released for organic reactions. This work provides a new approach for the synthesis of pure interhalogens and demonstrates the potential applications of MOF crystal vessels in reactions.

CHINESE JOURNAL OF STRUCTURAL CHEMISTRY (2023)

Article Chemistry, Medicinal

One-Dimensional Heterobimetallic Au/Ag Coordination Polymer Showing a Selective, Reversible, and Visible Vapor-Chromic Photoluminescent Response toward Methanol

Mengyao Feng, Fuyuan Liu, Ningwen Yang, Jiayao Yu, Wei Yang, David James Young, Xiang-Qian Cao, Hong-Xi Li, Zhi-Gang Ren

Summary: A heterobimetallic coordination polymer [Au4(dppmt)4(AgCl)2]n (1) incorporating an in situ generated P-S ligand (dppmtH) was synthesized. The structure of 1 contains a one-dimensional helical Au-Au chain. Coordination polymer 1 exhibited a rapid, selective, reversible, and visible vapor chromic response on exposure to methanol (MeOH) vapor.

ACS MEDICINAL CHEMISTRY LETTERS (2023)

Article Chemistry, Inorganic & Nuclear

Reversible Single-Crystal-to-Single-Crystal Transformations between Nanoscale 2D Nanosheets and 3D Metal-Organic Frameworks

Mengling Zhang, Yu Ge, Zheng Qin, Qilei Jiang, Xianggang Huang, Yan Hou, Yingxin Liu, Xueqin Cao, Jian-Ping Lang, Hongwei Gu

Summary: This study demonstrates reversible single-crystal-to-single-crystal (SCSC) transformations between nanoscale three-dimensional ZIF-67 and two-dimensional Co-LDH. The resulting Co-LDH materials show superior oxygen evolution reaction performance, indicating their potential value in crystal synthesis and resource recycling.

INORGANIC CHEMISTRY (2023)

Article Chemistry, Multidisciplinary

Synthesis, Structural Characterization, and Photochemical [2+2] Cycloaddition of a Coordination Polymer: Multiweek Inorganic-Organic Chemistry Experiments

Yu-Xuan Hong, Meng-Fan Wang, Yu Ge, Hong Yu, Chun-Yan Ni, Wei-Yi Chen, Pierre Braunstein, Jian-Ping Lang

Summary: The solid-state [2 + 2] photocycloaddition experiment introduced in this study provides senior undergraduate students with a comprehensive understanding of coordination chemistry, organic chemistry, structural chemistry, and supramolecular chemistry. This experiment not only strengthens students' experimental skills, but also broadens their research horizon and promotes rigorous thinking in a laboratory course.

JOURNAL OF CHEMICAL EDUCATION (2023)

Article Chemistry, Multidisciplinary

Introducing Frustrated Lewis Pairs to Metal-Organic Framework for Selective Hydrogenation of N-Heterocycles

Ze-Ming Xu, Zhuoyi Hu, Yali Huang, Shu-Jin Bao, Zheng Niu, Jian-Ping Lang, Abdullah M. Al-Enizi, Ayman Nafady, Shengqian Ma

Summary: Hydrogenated nitrogen heterocyclic compounds are critical in various industries. Previous studies on the partial hydrogenation of these compounds have focused on costly and toxic precious metal catalysts. This research introduces a novel P/B type MOF-FLP catalyst achieved through a solvent-assisted linker incorporation approach, which significantly enhances catalytic hydrogenation reactions.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

Article Biochemistry & Molecular Biology

A Multiple Stimuli-Responsive Ag/P/S Complex Showing Solvochromic and Mechanochromic Photoluminescence

Jia-Jun Yan, Yu Wu, Weijia Zhai, Ningwen Yang, Hong-Xi Li, Wei Yang, Chengrong Lu, David James Young, Zhi-Gang Ren

Summary: The reaction of CF3COOAg, 3-bdppmapy and HTZ in CH2Cl2/MeOH resulted in a dinuclear Ag/P/S complex [Ag-2(TZ)(2)(3-bdppmapy)(2)]& BULL;xSol (1 & BULL;xSol). Crystals of 1 & BULL;xSol converted to 1 & BULL;2MeOH in air at room temperature and further to 1 under vacuum upon heating. The solid-state, room-temperature photoluminescent emission of 1 & BULL;xSol (510 nm) shifted to 494 nm (1 & BULL;2MeOH) and 486 nm (1).

MOLECULES (2023)

Article Chemistry, Organic

Visible-light-initiated nickel-catalyzed amination of aryl halides using thioxanthen-9-one as a photocatalyst

Da-Liang Zhu, Jie Li, David James Young, Yanqing Wang, Hong-Xi Li

Summary: This paper presents a mild strategy for aminating aryl halides with anilines using dual photoredox and nickel catalysis. Thioxanthen-9-one, an inexpensive and readily available compound, greatly enhanced this cross-coupling reaction, yielding a diverse range of diarylamines in good yields (41-93%) at room temperature. The reaction could be performed under compact fluorescent lamp light or sunlight and was tolerant of various functional groups. It was successfully applied to the synthesis of natural products and drug molecules, even at a gram-scale. The mechanism involves several steps including oxidative addition, transmetalation, energy transfer, and reductive elimination.

ORGANIC CHEMISTRY FRONTIERS (2023)

Article Chemistry, Inorganic & Nuclear

A PN(Pz)P ligand protected Au2Cu2 complex for photoluminescent ultra-low humidity detection with reversible single-crystal-to-single-crystal transformations

Shengnan Hu, Sisi Yan, Yuanyuan Hu, David James Young, Hong-Xi Li, Chengrong Lu, Jing-Hui He, Zhi-Gang Ren

Summary: Reliable and sensitive detection of sub-ppm level, ultra-low humidity is critical for a number of important technologies. We report a heteronuclear Au2Cu2 cluster complex that can undergo reversible transformations and has photoluminescent properties in different environments. The crystals of the complex can detect ultralow humidity of 0.21 ppm (w/w).

INORGANIC CHEMISTRY FRONTIERS (2023)

Article Chemistry, Inorganic & Nuclear

Heteroleptic copper(i) complexes [Cu(dmp)(N∧P)]BF4 for photoinduced atom-transfer radical addition reactions

You-Hui Zhao, Hai-Yan Li, David James Young, Xiangqian Cao, Da-Liang Zhu, Zhi-Gang Ren, Hong-Xi Li

Summary: Earth-abundant copper(I) coordination complexes have been developed as visible-light photocatalysts for the intermolecular atom-transfer radical addition reactions. Four heteroleptic bis-chelate Cu(I) complexes were synthesized and showed broad absorption in the visible spectrum. These complexes facilitated efficient reactions with CBr4, CCl3Br, and CHI3, yielding high product yields up to 91%. The substitution on the phpz ligand had a significant impact on the absorption, emission, redox potential, and photocatalytic activity.

DALTON TRANSACTIONS (2023)

Article Chemistry, Inorganic & Nuclear

One-Dimensional Heterobimetallic Au/Ag Coordination Polymer Showing a Selective, Reversible, and Visible Vapor-Chromic Photoluminescent Response toward Methanol

Mengyao Feng, Fuyuan Liu, Ningwen Yang, Jiayao Yu, Wei Yang, David James Young, Xiang-Qian Cao, Hong -Xi Li, Zhi-Gang Ren

Summary: A heterobimetallic coordination polymer [Au-4(dppmt)(4)(AgCl)2(]) n (1) with an in situ generated P-S ligand (dppmtH) was synthesized. The structure of 1 contains a helical Au-Au chain connected by [Au(2()dppmt)(2)] dimers. Upon excitation at 343 nm, 1 exhibited cyan phosphorescent emission at QY = 22.3% and t = 0.78 μs. Coordination polymer 1 exhibited a rapid, selective, reversible, and visible vaporchromic response on exposure to methanol vapor, with its emission shifting to a more intense green at QY = 46.8% and t = 1.24 μs.

INORGANIC CHEMISTRY (2023)

Article Chemistry, Multidisciplinary

Two-dimensional Cd3-based metal-organic frameworks with halogen bonding sites for the uptake of I2

Zhi-Hao Zhang, Jia-Lu Ge, Yan Li, Qing Li, Pin-Pin Ma, Xiao-Yan Tang, Wen-Hua Zhang, David J. Young

Summary: Developing porous materials for efficient capture of I-2 is important for the sequestration and storage of radioactive iodine towards clean nuclear energy. In this study, three structurally identical two-dimensional (2D) metal-organic frameworks (MOFs) were prepared, and one of the MOFs showed the highest adsorption capacity for I-2.

CRYSTENGCOMM (2023)

Article Chemistry, Physical

Screening of transition metal and boron atoms co-doped graphdiyne catalysts for electrocatalytic urea synthesis

Weichan Zhong, Dixing Chen, Yuting Wu, Jingxiu Yue, Zhangfeng Shen, Hong Huang, Yangang Wang, Xi Li, Jian-Ping Lang, Qineng Xia, Yongyong Cao

Summary: This study proposes a systematic approach to screen efficient double-atom catalysts (DACs) for urea production, using nitrogen and carbon dioxide as precursors, with the help of density functional theory (DFT). The results show that co-doped graphdiyne with CrB and MnB double atoms emerge as potential electrocatalysts for urea production, displaying low energy barriers and the capability to suppress the formation of unwanted by-products. The study establishes a theoretical framework for the evaluation of DACs in electrocatalytic urea synthesis.

JOURNAL OF COLLOID AND INTERFACE SCIENCE (2024)

Article Biochemistry & Molecular Biology

Enhanced mechanical strength of vortex fluidic mediated biomass-based biodegradable films composed from agar, alginate and kombucha cellulose hydrolysates

Shan He, Yixiao Wu, Yang Zhang, Xuan Luo, Christopher T. Gibson d Jingrong Gao, Jingrong Gao, Matt Jellicoe, Hao Wang, David J. Young, Colin L. Raston

Summary: Biodegradable cellulose films derived from kombucha, processed using a vortex fluidic device, show increased mechanical strength due to intense micromixing and high shear stress of the liquid film. The films retain their biodegradability and degrade within 5 days.

INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES (2023)

暂无数据