MONATSHEFTE FUR CHEMIE
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2023
·Vol. 154
·期 10
·1189-1195
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IF 1.8
Wang Peng,Shi Huibing,Feng Baolin,Zhao Deming,Wu Haigang
The Ru-catalyzed highly selective alkoxycarbonylation of allenes with aliphatic alcohols (also as solvent) allow to produce useful α , β -unsaturated esters in good to excellent yields at 70 °C. Efficient regioselectivity could be controlled in the presence of N-ligands while the P-ligands had no influence on the conversion of substrates and the chemo/regioselectivity of target products. By involving N-ligand 4,7-dimethyl-1,10-phenanthroline in the catalytic system, α , β -unsaturated esters were obtained with high conversion and chemo/regioselectivity (conversion up to 99%, chemical selectivity up to 99%, regioselectivity of branched ester/linear ester up to 89/11). Graphical abstract
研究领域:
有机化学
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催化化学
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DOI
高影响因子
TETRAHEDRON
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2017
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IF 2.651
Shi-Yuan Liu,Lin-Yan Xu,Chun-Yu Liu,Zhi-Gang Ren,David James Young,Jian-Ping Lang
An efficient catalytic system containing [RuCl 2 (η 6 -p-cymene)] 2 and one P,N ligand, N-diphenylphosphino-2-aminopyridine ( L1 ) was loaded in catalyzing the alkylation of ketones with primary alcohols for a diverse array of substrates. Other five P,N ligands based on pyridin-2-amine and pyrimidin-2-amine were also examined in this reaction to explore the influence of steric hindrance and electronic effects. Monitoring by 1 H NMR and ESI-MS reveals a stable cationic L1 -coordinated ruthenium hydride intermediate, identified as [Ru(η 6 -p-cymene)(κ 2 - L1 )H] + . Organic intermediates consistent with a three-step dehydrogenation , alkylation and hydrogenation pathway were also observed. The final step in this reaction, the ruthenium-catalysed transfer hydrogenation reduction of α,β-unsaturated ketone with benzyl alcohol was performed separately.
研究领域:
有机化学
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催化化学
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DOI
高影响因子
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
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2014
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IF 3.679
Sheng-Jie Chen,Yong-Qi Li,Yong-Yong Wang,Xiao-Li Zhao,Ye Liu
The ionic hybrid P,N-ligands of 1 and 2 have been synthesized as one type of unconventional tertiary phosphines with the advantages of both the π-accepting ligands and the hemilabile ligands. The corresponding ionic Rh(I)-complexes of 1A and 2A proved to be more efficient catalysts for hydroformylation of 1-octene over isomerization than the traditional Rh I (acac)(CO)(PPh 3 ), due to the π-backdonation interaction in Rh → P linkage and the hemilabile ligation of N,P-coordinating sites to Rh-center. The in situ high-pressure FT-IR analysis indicated that: (1) the formation and lifetime of the active Rh H species (2047 cm −1 ) derived from 1A are facilitated by the presence of ligand 1 ; (2) the formation of the active Rh H species is depressed without the aid of the P,N-hemilabile ligation; and (3) the active Rh H species derived from Rh I (acac)(CO)(PPh 3 ) is unstable and susceptible to the formation of the inactive carbonyl-bridged Rh-dimer.
研究领域:
化学
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催化反应
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DOI
高影响因子
ANALYTICA CHIMICA ACTA
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2025
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IF 6
Xiaoqian Yuan,Yuchen Cui,Yaqin Nan,Ruijun Tang,Xinru Wang,Yanmei Xu,Xinghua Jin,Yiwen Wang,Ding Cheng,Youxin Li
Background Cyclodextrins (CDs) and their derivatives have been widely used as chiral selectors in HPLC. However, many derivatized CDs lack specificity for certain drugs and often exhibit limited resolution. Furthermore, their synthesis typically involves complex multi-step procedures, hindering scalability and cost-efficiency. To overcome these limitations, this study aims to develop a simple and scalable boric acid-modified β-cyclodextrin polymer (BA-β-CDP), targeting chiral substances with O/N atoms in chiral and/or adjacent carbons. Results BA-β-CDP was synthesized on a large scale using inexpensive reagents and a random substitution strategy, avoiding tedious protection-purification steps. Structural and chromatographic compatibility was confirmed by nine characterization techniques. In HPLC using the chiral mobile-phase additive (CMPA) method, BA-β-CDP enabled the efficient separation of 25 racemates. Among them, 24 achieved complete or baseline separation, and 10 exhibited resolution (Rs) values > 10. Typical cases included bisoprolol (Rs = 48.19), propranolol (Rs = 45.50), chlorpheniramine (Rs = 38.36), and metoprolol (Rs = 20.26). Additionally, the material demonstrated excellent batch-to-batch reproducibility, recyclability, and reusability. Significance and novelty This work presents a practical and cost-effective chiral selector. The synergistic mechanism offers strong and specific recognition toward chiral substances with O/N atoms in chiral and/or adjacent carbons. This approach represents a novel strategy for efficient and economical HPLC-based enantioseparation using widely accessible materials and methods.
研究领域:
分析化学
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药物化学
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手性技术
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分子识别
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药剂学
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有机合成
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF MEDICINAL CHEMISTRY
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2013
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IF 5.614
Rui Cao,Junli Jia,Xiaochuan Ma,Ming Zhou,Hao Fei
The cellular behavior and toxicity effect of organometallic complexes depend largely on their peripheral ligands. In this study, we have synthesized a series of novel luminescent cationic iridium(III) complexes by tuning the ancillary N∧N ligand based on a structure [Ir(ppy)2(N∧N)]+ (ppy = 1-phenyl-pyridine; N∧N = 2,2′-bipyridine (bpy, 1) or phenanthroline (phen, 2) or 4,7-diphenyl-1,10- phenanthroline (DIP, 3)). As the size of coordinated N∧N ligand increases, absorbance/emission efficiency, quantum yields, lipophilicity, and cell uptake rates of the complexes also increase, in a general order: 3 > 2 > 1. All three complexes display anticancer activity, with 3 exhibiting the highest cellular uptake efficiency and the greatest cytotoxic activities in several cancer cell lines with IC50s lower than that of cisplatin. Because of its strong hydrophobic nature, the death inducer 3 was found to accumulate favorably to endoplasmic reticulum (ER) and to cause ER stress in cells. The fast cytosolic release of calcium from stressed ER disturbed the morphology and function of mitochondria, initiating an intrinsic apoptotic pathway. Understanding of the cell death mechanism would help further structure–activity optimization on these novel Ir(III) complexes as emerging cancer therapeutics.
研究领域:
化学
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材料科学
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肿瘤学
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细胞生物学
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药学
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DOI
PubMed
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
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2025
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IF 3.6
Lei Xu,Hao Sun,Xuefeng Tan,Dong Li,Gen-Qiang Chen,Xumu Zhang
A series of ferrocene-based chiral multidentate P,P,N,N-ligands were successfully designed and synthesized. They can be directly prepared via a one-step nucleophilic substitution reaction from (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl] ethyl acetate [(SC,RFC)-BPPFOAc]. Their ruthenium complexes were used in the asymmetric hydrogenation of 2-pyridyl ketones under mild conditions, the target chiral 1-aryl- or 1-alkyl-(pyridine-2-yl)methanols were obtained with high yields and excellent enantioselectivities. The synthetic utility of this reaction was demonstrated through its utilization in the preparation of key intermediates for a RAS inhibitor and the antihistamine drug Carbinoxamine.
研究领域:
有机化学
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不对称催化
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药物化学
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配位化学
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产品关联
DOI
PubMed
高影响因子
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