Article
Chemistry, Inorganic & Nuclear
Panisha Nayak, Manisha Nayak, Subhajit Kar, Sanjib Kar
Summary: A practical and efficient protocol for the oxidative cleavage of olefinic bonds, especially in arylated olefins, has been demonstrated. The study successfully synthesized an oxo[5,10,15-tris(4-nitrophenyl)corrolato]vanadium (IV) complex and established the existence of two tautomeric forms of this complex in solution. The complex, in the presence of H2O2, cleaves olefinic bonds to yield the corresponding aldehydes, offering good yields and excellent selectivity.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xiaoxue Li, Hangzhou Hua, Yonghong Liu, Lei Yu
Summary: Catalyzed by Se/Fe via hybrid mechanisms, the carbon-carbon double bond in alkenes can break to produce carbonyls under mild conditions. Using O-2 as a partial oxidant, the amount of H2O2 employed can be reduced (90 mol% vs 250 mol%) to avoid peroxide residues, making the process safer for operation.
Article
Chemistry, Multidisciplinary
Dan E. Wise, Emma S. Gogarnoiu, Alana D. Duke, Joshua M. Paolillo, Taylor L. Vacala, Waseem A. Hussain, Marvin Parasram
Summary: We report a new method for anaerobic cleavage of alkenes into carbonyl compounds using nitroarenes as oxygen transfer reagents under visible light. This approach is a safe and practical alternative to traditional oxidative cleavage methods. Mechanistic studies show that the transformation occurs through direct photoexcitation of the nitroarene followed by nonstereospecific radical cycloaddition with alkenes. Various alkenes with oxidatively sensitive functionalities can be efficiently and selectively cleaved anaerobically to generate carbonyl derivatives.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Qiangwen Fan, Honglei Zhang, Dawei Liu, Chunpei Yan, Haibo Zhu, Zongbo Xie, Zhanggao Le
Summary: Here, we reported a facile and accessible visible-light-driven photocatalytic protocol for the oxidative cleavage of C C bonds to form carbonyl compounds using CsPbBr3 nanocrystals as photocatalysts. This catalytic system is applicable to a wide range of terminal and internal alkenes. Mechanism studies revealed that a single-electron transfer process involving the superoxide radical (O-2 (& BULL;-)) and photogenerated holes played a crucial role in this transformation. DFT calculations showed that the reaction started with the addition of O-2 (& BULL;-) to the terminal carbon atom of the C C bond and proceeded to release one molecule of formaldehyde through the formation of a [2 + 2] intermediate; the latter step being the rate-determining process.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Hafsa Karroum, Sergey Chenakin, Sergei Alekseev, Viacheslav Iablokov, Yizhi Xiang, Vincent Dubois, Norbert Kruse
Summary: This study presents a one-step-one-pot synthesis of chain-lengthened aliphatic amines and nitriles using potassium-promoted Co/MnOx catalysts, showing that the reaction can be tuned by adjusting the H-2/CO ratio. Additionally, the addition of NH3 strongly favors the formation of chain-lengthened olefins over alkanes.
Article
Chemistry, Organic
Xiaoguang Yue, Yani Ouyang, Jiashun Zhu, Jingfang Yue, Jiehai Peng, Wanmei Li
Summary: A method of oxidative cracking of olefins' C=C bonds promoted by NaN3 in water was developed, without the use of a photocatalyst. Under blue light irradiation, cheap olefins can be converted to aldehydes or ketones with moderate to good yields at room temperature. Experimental results suggest that NaN3-O-2 charge-transfer complexes may be formed during the reaction, which are then oxidized and cracked to form aldehydes or ketones.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Xinglin Wang, Yuanyuan Li, Zhaohui Li
Summary: ZnIn2S4 catalyzed oxidative cleavage of olefins to produce aldehydes/ketones under visible light using air and thiol initiators, provides a novel pathway for organic synthesis. Moreover, direct production of different acetals from olefins is achieved, offering a new protocol in the field.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Jiantao Zhang, Weiming Zhu, Peng Zhou, Cui Chen, Weibing Liu
Summary: A catalyst-free 1,2-difunctionalization of 1,3-dienes with CHCl3 and TBHP in the presence of NEt3 has been developed, giving the desired dichloromethylhydroxylation products. Various substituents on the aryl ring were tolerated and moderate to good yields of the corresponding products were obtained. When Na2CO3 was used as the base, the formation of the key α-amino radical was inhibited, resulting in the formation of 1,2-peroxyhydroxylation products. This method provides an effective and functional group tolerant strategy for diene 1,2-difunctionalization, allowing for further functionalization and modification of synthetic molecules.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Gong-Qing Liu, Wei Yi, Peng-Fei Wang, Ji Liu, Meng Ma, Da-Yun Hao, Liang Ming, Yong Ling
Summary: A novel reaction system has been developed for the oxidative coupling of diselenides with vinylarenes under visible light irradiation, providing a range of alpha-aryl and alpha-alkyl selenomethyl ketones with high yields and excellent compatibility with various functional groups. The use of a green solvent, air as an oxidant, and natural sunlight as a sustainable energy source sets this protocol apart from previous methods, making it an attractive option for the synthesis of medicinal and agrochemical compounds.
Article
Chemistry, Multidisciplinary
Jia Li, Leli Zeng, Zheng Wang, Hengxing Chen, Shuo Fang, Jinquan Wang, Chao-Yun Cai, Enming Xing, Xinxing Liao, Zhi-Wei Li, Charles R. Ashby, Zhe-Sheng Chen, Hui Chao, Yihang Pan
Summary: RuZ, a cycloruthenated complex, self-assembles into nanoaggregates in cell culture medium, leading to high intracellular concentrations in multi-drug resistant (MDR) cancer cells. It decreases oxygen consumption, inhibits glycolysis, lowers ATP levels, increases retention in MDR cells, induces oxidative stress and apoptosis. Proteomic analysis shows RuZ decreases glycolysis and mitochondrial respiration proteins while increasing apoptosis-related proteins. It inhibits proliferation of 35 cancer cell lines, including drug-resistant ones, and is effective in doxorubicin-resistant mouse tumor xenografts.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Physical
Ruoxuan Liang, Jiwei Li, Yaowei Wang, Zhaoxia Zhang, Bo Luan, Jianjun Liu, Shuya Qian, Shaolong Wan, Deming Zhao, Haifeng Xiong, Shuai Wang, Jingdong Lin, Yong Wang
Summary: In this study, we found that hexagonal boron nitride (h-BN) demonstrates good selectivity and activity in the oxidative dehydrogenation reaction of n-hexane. Low temperatures and oxygen-rich environments favor the selective hydrogen abstraction from C-H bonds, and the presence of gas phase free radicals improves the reaction rate. Additionally, an anomalous relationship exists between the conversion of n-hexane and reaction temperature.
APPLIED CATALYSIS A-GENERAL
(2022)
Article
Multidisciplinary Sciences
Qinglong Shi, Meichen Xu, Rui Chang, Devenderan Ramanathan, Beatriz Penin, Ignacio Funes-Ardoiz, Juntao Ye
Summary: A metal-free platform using peptide- or sugar-derived chiral thiols and deuterium oxide enables asymmetric open-shell deuteration at non-benzylic positions. This approach allows for multiple types of deuterofunctionalization reactions of exocyclic olefins and achieves high levels of enantioselectivity and deuterium incorporation.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Galal A. Nasser, M. H. M. Ahmed, Mochamad A. Firdaus, Mohammed A. Sanhoob, Idris A. Bakare, E. N. Al-Shafei, M. Z. Al-Bahar, A. N. Al-Jishi, Z. H. Yamani, Ki-Hyouk Choi, Oki Muraza
Summary: Nano BEA zeolite catalysts were synthesized and modified by desilication and Co ion-exchange, altering the acidity of the catalysts. The conversion and yield of light olefins increased with higher reaction temperatures in the range of 400 to 600 degrees Celsius.
Article
Chemistry, Inorganic & Nuclear
Tuhin Ganguly, Abhijit Bera, Anuj Baran Chakraborty, Amit Majumdar
Summary: A new and efficient catalytic hydrolysis method for aliphatic and aromatic thiolates under ambient conditions is presented. The previous stoichiometric reaction product is shown to act as an efficient catalyst for the hydrolysis of a broad range of thiolates, producing alcohols/phenols. The reaction proceeds in DMF at room temperature.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yichen Sun, Zhibin Hu, Jing Peng, Qixue Qin, Ning Jiao
Summary: The Baeyer-Villiger oxidation is a valuable reaction for converting ketones into esters or lactones. In this study, a novel and efficient approach utilizing I-2 as a catalyst for the oxidative rearrangement of cyclobutenones was presented, resulting in the synthesis of furan-2(5H)-one. Dimethyl sulfoxide (DMSO) was used as a greener oxidant and source of oxygen. The reaction proceeded smoothly with catalytic amounts of iodine, yielding lactones in good yields. Compared to conventional Baeyer-Villiger oxidation reactions, the use of DMSO offers a safer and more versatile alternative.