Article
Chemistry, Multidisciplinary
Jun Xu, Yilan Zhang, Xiaoguang Yue, Jie Huo, Daokai Xiong, Pengfei Zhang
Summary: This method describes a practical and sustainable way to synthesize aldehydes, ketones, and carboxylic acids from inexpensive olefinic feedstock. It utilizes commercially available and inexpensive tetrahydrofuran as the additive, molecular oxygen as the sole oxidant, and water as the solvent. A radical mechanism was found to be responsible for the oxidation reaction, enabling moderate-to-good yields of carbonyl compounds from a wide range of substituted alkenes.
Article
Chemistry, Multidisciplinary
Xinwei Li, Zengrui Cheng, Jianzhong Liu, Ziyao Zhang, Song Song, Ning Jiao
Summary: In this study, we demonstrated an Fe-assisted regioselective oxidative desaturation of amides, providing an efficient approach to enamides and beta-halogenated enamides.
Article
Multidisciplinary Sciences
Zhankai Liu, Ziyi Liu, Jie Fan, Wen-Duo Lu, Fan Wu, Bin Gao, Jian Sheng, Bin Qiu, Dongqi Wang, An-Hui Lu
Summary: The in-situ formed olefins in the oxidative dehydrogenation (ODH) of alkane over boron nitride (BN) catalysts can actively promote the conversion of parent alkane by interacting with hydroperoxyl and alkoxyl radicals. Isotope tracer studies provide evidence of deep-oxidation of olefins occurring in the ODH reaction over BN. Ethane can be activated at a lower temperature by propane-derived olefins through co-feeding alkane mixture strategy. This work reveals the pathway of the ODH reaction over BN and offers insights into efficient olefin production.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Xun Wu, Akalanka Tennakoon, Ryan Yappert, Michaela Esveld, Magali S. Ferrandon, Ryan A. Hackler, Anne M. LaPointe, Andreas Heyden, Massimiliano Delferro, Baron Peters, Aaron D. Sadow, Wenyu Huang
Summary: This study investigates the effects of Pt nanoparticle size on the activity and selectivity of polyethylene hydrogenolysis. The results show that the smallest Pt nanoparticles exhibit the highest activity, while the three different-sized Pt nanoparticles have equivalent selectivity. Furthermore, the study also reveals that the mesoporous pores template the formation of a C 23 -centered distribution of hydrocarbons. These findings provide a framework for catalyst design by separating the carbon-carbon bond cleavage activity from the selectivity for chain lengths of the products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Geng Sun, Philippe Sautet
Summary: This article explores the fluxionality of active sites in nanoclusters, highlighting the significant roles of plastic and elastic fluxionality in efficient reaction pathways. Low-energy metastable isomers formed by plastic fluxionality can exhibit high reactivity, while elastic fluxionality induces substantial structural deformations of the active site, resulting in low activation energies and high catalytic activity.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Aaron Sattler, Michele Paccagnini, Elaine Gomez, Randall J. Meyer, Sara Yacob, Henry Klutse, Michael Caulfield, Yuan Gao
Summary: This study focuses on the application of ethane dehydrogenation in membrane reactors, evaluating the adaptability of catalysts to new gas-phase compositions by simulating hydrogen removal conditions. The results indicate that the catalyst is adversely affected by reactions under hydrogen removal conditions, limiting ethylene yields.
ENERGY & ENVIRONMENTAL SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Kai Zheng, Yang Wu, Zexun Hu, Xingchen Jiao, Li Li, Yuan Zhao, Shumin Wang, Shan Zhu, Wenxiu Liu, Wensheng Yan, Yongfu Sun, Yi Xie
Summary: This study presents a positively charged metal cluster catalyst anchored on a porous carbon aerogel for the selective partial photooxidation of methane into value-added chemicals. Experimental results demonstrate high CH3OOH selectivity and productivity of the catalyst under mild conditions.
Article
Chemistry, Multidisciplinary
Jeffrey Bruffaerts, Inbar Kesten, Keren Buhnik-Rosenblau, Anthony Cohen, Nurit Edri, Morgan Cormier, Yuanfei Zhang, Guo-Ming Ho, Itai Massad, Hila Halfon-Verner, Yechezkel Kashi, Ilan Marek
Summary: A two-step sequential strategy involving a biocatalytic dehydrogenation/remote hydrofunctionalization is reported for selectively converting linear alkanes into valuable functionalized aliphatic derivatives. The dehydrogenation is conducted by a mutant strain of Rhodococcus bacteria, and the resulting alkenes are further functionalized through a metal-catalyzed hydrometalation/migration sequence with various electrophiles. This combined biocatalytic and organometallic approach enables high-yielding site-selective functionalization of unreactive primary C-H bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Chenxi Wen, Ting Li, Zheng Huang, Qi-Kai Kang
Summary: Preparing valuable olefins from cheap and abundant alkane resources has long been a challenging task in organic synthesis. Homogeneous transition metals catalyzed dehydrogenation of alkanes has attracted much attention for its excellent catalytic activities. In this review, we discuss recent development of base metal catalyzed alkane dehydrogenation under oxidative conditions and their application in constructing complex molecules.
Article
Engineering, Environmental
Yushan Wu, Yawen Tong, Heng Liang, Jiebang Peng, Xiang-Kui Gu, Mingyue Ding
Summary: Small Pd nanoparticles encapsulated in a metal-organic framework exhibited high catalytic performance for the conversion of 5-hydroxymethylfurfural to 2,5-dihydroxymethyl-tetrahydrofuran. The catalyst achieved a conversion yield of 95.8% and a production rate of 85.1 h(-1) under mild conditions with 1 MPa H-2 pressure. The superior catalytic activity was attributed to the presence of small Pd nanoparticles that provided stable defective sites for the reaction.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yunrui Zhang, Dong-Hui Yang, Shanlin Qiao, Bao-Hang Han
Summary: The study developed a highly efficient catalyst for CO2 cycloaddition reaction by covalently modifying ionic liquids to covalent organic frameworks and utilizing the electrostatic interaction between polyoxometalates (POMs) and ionic liquids. The catalyst showed high catalytic activity under mild conditions and retained its performance after multiple uses, attributed to the synergistic effect of ionic liquids, POMs, and COFs.
Article
Chemistry, Multidisciplinary
Jisheng Xu, Chengxiang Shi, Shuguang Zhang, Qiancheng Zheng, Lun Pan, Xiangwen Zhang, Ji-Jun Zou
Summary: Non-oxidative ethane dehydrogenation to produce ethene is a promising route, and PtSn supported catalysts with different Zr promoters were investigated in this study. Strong interaction between ZrO2 and PtSn species promotes initial reactivity, while moderate interaction with framework Zr benefits the dispersion of metal particles and stabilization of metal species. The optimal PtSn/ZrM catalyst achieved outstanding initial ethane conversion and ethene selectivity, with improved coking tolerance and stability.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Liu Yifeng, Wang Liang, Xiao Feng-Shou
Summary: Selective oxidation of methane to methanol has been a dream reaction, but faces challenges due to the strong C-H bond and easy overoxidation of the methanol product. Strategies using oxidants such as hydrogen peroxide and a mixture of oxygen and hydrogen have been developed to improve methanol productivity at mild temperatures. Effective catalysts, including supported metal nanoparticles, colloidal metal nanoparticles, and metal@zeolites, have shown significant achievements. The zeolite fixed metal nanoparticle structure has been found to enhance the reaction by facilitating the formation and enrichment of peroxide intermediates, which could guide the development of more efficient catalysts.
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
(2022)
Article
Chemistry, Organic
Hailong Zhao, Aidong Shan, Yunshi Liang, Haiting Wu, Yiting He, Huihong Chen, Jiaxin Zeng, Jiangyong Gu, Jian-Ping Song, Hong Qiu, Jing Zhang
Summary: Protein citrullination, a type of protein post-translational modification, has been hindered by the use of strongly acidic conditions. In this study, a biocompatible method based on o-boron-assisted citrulline modification was developed, enabling selective and mainly irreversible modification of citrulline residues under neutral conditions. This method provides a valuable tool for studying protein citrullination.
Article
Geosciences, Multidisciplinary
Xin Yang, Yapei Li, Yajie Wang, Haiyan Zheng, Kuo Li, Ho-kwang Mao
Summary: Research shows that under high pressure and high temperature conditions, n-hexane and cyclohexane undergo phase transitions and decompose into hydrogenated graphitic carbon, with n-hexane exhibiting higher stability compared to cyclohexane.
GEOSCIENCE FRONTIERS
(2021)
Article
Polymer Science
Louise Breloy, Vlasta Brezova, Jean-Pierre Malval, Agustin Rios de Anda, Julie Bourgon, Takashi Kurogi, Daniel J. Mindiola, Davy-Louis Versace
Article
Chemistry, Applied
Zhipeng Zheng, Oleksandra S. Trofymchuk, Takashi Kurogi, Elena Varela, Daniel J. Mindiola, Patrick J. Walsh
ADVANCED SYNTHESIS & CATALYSIS
(2020)
Article
Chemistry, Inorganic & Nuclear
Takashi Kurogi, Daniel J. Mindiola
Article
Chemistry, Multidisciplinary
Mehrafshan G. Jafari, Yerin Park, Bimal Pudasaini, Takashi Kurogi, Patrick J. Carroll, David M. Kaphan, Jeremy Kropf, Massimiliano Delferro, Mu-Hyun Baik, Daniel J. Mindiola
Summary: This study presents the synthesis of a novel vanadium complex, investigating its electronic ground state using computational and experimental methods. The research reveals the mechanism of P-atom transfer and the nature of the low-valent vanadium ion in the complexes 2 and 4.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sobi Asako, Ikko Takahashi, Takashi Kurogi, Yoshiaki Murakami, Laurean Ilies, Kazuhiko Takai
Summary: The combination of a sodium dispersion in paraffin oil and 1,3-dimethyl-2-imidazolidinone enables the Birch-type reduction of a variety of arenes with high yields, selectivity, and tolerance of functionality.
Article
Chemistry, Organic
Shuo Wang, Atsushi Kaga, Takashi Kurogi, Hideki Yorimitsu
Summary: In this study, treatment of arylcyclopropanecarboxamides with a sodium dispersion in the presence of methoxypinacolborane as a reduction-resistant electrophile was investigated. The results showed that the reaction led to the reductive cleavage of the cyclopropane ring followed by instant trapping with the boron electrophile, resulting in the formation of enolates of gamma-aryl-gamma-borylalkanamides. The enolates could further react with a different electrophile to produce the corresponding a-substituted amides with anti selectivity.
Article
Chemistry, Multidisciplinary
Takashi Kurogi, Kenta Uchida, Kazusa Wakamatsu, Kazuhiko Takai
Summary: This article attempts to generate early transition metal methylene species through the transmetallation of zinc mu-methylene species with various metal chlorides. A dinuclear chromium mu-methylene complex is successfully isolated and characterized by X-ray crystallography, and the carbene/alkyne metathesis of the chromium methylene complex with 1,6-enyne is demonstrated.
Article
Chemistry, Multidisciplinary
Kazuhira Miwa, Shinobu Aoyagi, Toru Amaya, Takahiro Sasamori, Shogo Morisako, Takashi Kurogi, Hideki Yorimitsu
Summary: The curved and π-conjugated surface of bowl-shaped corannulene has been multiply methylated through in-situ iterative reduction/methylation sequences, resulting in exo-di-, -tetra-, and -hexamethylated corannulenes. Various analytical techniques have been used to reveal the molecular structures of the multimethylated corannulenes and the sequence of the multimethylation. This work has the potential to contribute to the controlled synthesis and characterization of multifunctionalized fullerenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Ziwei Zhang, Fumiya Takahashi, Takashi Kurogi, Hideki Yorimitsu
Summary: The preparation of vinylic lithium reagents from vinylic halides is common in organic synthesis, but not always easy. This study proposes a new method using silyl enolates of alkyl aryl ketones, which provides readily available and efficient vinylic lithium species. The reductive transformation of electron-rich silyl enolates has significant potential for various applications in organic synthesis, serving as an alternative to the Shapiro reaction.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Takashi Kurogi, Keiichi Irifune, Kazuhiko Takai
Summary: Carbon tetrabromide can be reduced with CrBr2 in THF to form a dinuclear carbido complex, which can react with aldehydes, alkenes, and terminal/internal alkynes to generate various products with different reactivities.
Article
Chemistry, Multidisciplinary
Takashi Kurogi, Keiichi Irifune, Takahiro Enoki, Kazuhiko Takai
Summary: Reduction of CCl4 by CrCl2 in THF led to the formation of a trinuclear chromium(iii) carbyne. The chlorocarbyne complex reacted with aldehydes to yield chloroallylic alcohols and terminal alkynes. Mechanistic study suggested two competing pathways via an alpha-chlorovinyl intermediate.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Takashi Kurogi, Kaito Kuroki, Shunsuke Moritani, Kazuhiko Takai
Summary: This study demonstrates the synthesis of a titanium methylene complex through transmetallation reaction and its reactivity towards esters and terminal olefins, leading to methylenation, olefin-metathesis, and olefin-homologation. Additionally, cyclopropanation by methylene transfer from the titanium complex was achieved using a 1,3-diene. The mechanistic study of the cyclopropanation reaction was also presented through density functional theory calculations.
Correction
Chemistry, Multidisciplinary
Masahito Murai, Ryuji Taniguchi, Takashi Kurogi, Shunsuke Moritani, Kazuhiko Takai
CHEMICAL COMMUNICATIONS
(2020)
Article
Chemistry, Multidisciplinary
Masahito Murai, Ryuji Taniguchi, Takashi Kurogi, Moritani Shunsuke, Kazuhiko Takai
CHEMICAL COMMUNICATIONS
(2020)
Article
Chemistry, Multidisciplinary
James T. Lukens, Ida M. DiMucci, Takashi Kurogi, Daniel J. Mindiola, Kyle M. Lancaster