Article
Chemistry, Multidisciplinary
Alexia N. Kim, Aurapat Ngamnithiporn, Michael D. Bartberger, Brian M. Stoltz
Summary: The first asymmetric trans-selective hydrogenation of 1,3-disubstituted isoquinolines has been developed, resulting in enantioenriched trans-tetrahydroisoquinolines in good yield with high enantioselectivity. Mechanistic studies reveal the crucial role of non-coordinating chlorinated solvents and halide additives in enabling trans-selectivity.
Article
Chemistry, Physical
Catherine Gazolla Santana, Michael J. Krische
Summary: Catalytic carbonyl reductive couplings facilitated by hydrogenation, transfer hydrogenation, and hydrogen autotransfer allow unsaturated hydrocarbons to substitute organometallic reagents for C-C bond formation without the need for stoichiometric metals, addressing issues of safety and challenges in large-scale implementation.
Article
Chemistry, Organic
Yu Nie, Qianjia Yuan, Feng Gao, Masahiro Terada, Wanbin Zhang
Summary: An efficient iridium-catalyzed double asymmetric hydrogenation of 2,5-dialkylienecyclopentanones is reported, delivering chiral 2,5-disubstituted cyclopentanones in excellent yields and stereoselectivities. The results suggest that the two C=C bonds were hydrogenated in a stepwise manner and the second stereocenter was controlled by the chiral catalyst and the chirality of monohydrogenated product. The hydrogenated products can be prepared on a gram-scale and are easily derivatized.
Article
Chemistry, Organic
Yu Nie, Qianjia Yuan, Feng Gao, Masahiro Terada, Wanbin Zhang
Summary: Herein, we report an efficient iridium-catalyzed double asymmetric hydrogenation of 2,5-dialkylienecyclopentanones, delivering the chiral 2,5-disubstituted cyclopentanones in excellent yields and stereoselectivities. The results of the kinetic experiments and control experiments indicated that the two C=C bonds were hydrogenated in a stepwise manner and the second stereocenter was synergistically controlled by the chiral catalyst and the chirality of monohydrogenated product. The hydrogenated products can be prepared on a gram-scale and are easily derivatized.
Article
Chemistry, Inorganic & Nuclear
Zheng Wang, Ning Ma, Xiaochi Lu, Ming Liu, Tian Liu, Qingbin Liu, Gregory A. Solan, Wen-Hua Sun
Summary: A series of manganese(i) carbonyl complexes with structurally related NN- and NNN-chelating ligands were synthesized and used as catalysts for transfer hydrogenation. The NN-systems based on N-R functionalized 5,6,7,8-tetrahydroquinoline-8-amines showed the highest catalytic activity in the conversion of acetophenone to 1-phenylethanol. The N-isopropyl derivative, Mn1, when combined with t-BuONa, achieved efficient reduction of acetophenone and various carbonyl substrates, with high TON values (up to 17,200; TOF of 3550 h(-1)). These findings support an outer-sphere mechanism for the hydrogen transfer and provide a sustainable alternative for producing alcoholic products from carbonyl substrates.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Yanhua Hu, Zhenfeng Zhang, Yangang Liu, Wanbin Zhang
Summary: Asymmetric hydrogenation is an effective method for preparing single enantiomer compounds, but the chemoselective and enantioselective hydrogenation of relatively inert unsaturated groups in substrates with multiple unsaturated bonds remains a challenge. A highly selective hydrogenation method for producing chiral propargylamines and enabling useful chemical transformations has been reported.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Peng Lu, Hongliang Wang, Yihui Mao, Xin Hong, Zhan Lu
Summary: Investigation on asymmetric hydrogenation of olefins is vital for the synthesis of pharmaceutical molecules and chemical industry. A cobalt-catalyzed enantioconvergent hydrogenation method has been developed for common minimally functionalized E/Z-olefin mixtures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Xuefeng Tan, Xiaoyan Hou, Torben Rogge, Lutz Ackermann
Summary: This study achieved the electrochemical three-component assembly of isoquinolines using ruthenium electro-catalyzed C-H/N-H functionalization, demonstrating a robust electrocatalysis with ample substrate scope, efficient electrooxidation, and an operationally friendly procedure. Furthermore, detailed mechanistic studies and unprecedented cyclovoltammetric analysis of a seven-membered ruthenacycle supported an unusual ruthenium(II/III/I) regime.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xinting Liang, Minjin Yoo, Tabitha Schempp, Saki Maejima, Michael J. Krische
Summary: By utilizing a series of complex synthetic methods, the key substructures of neaumycin B were successfully synthesized, which possess potent inhibitory activity against glioblastoma.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Ze Wang, Xianghua Zhao, Shiliang Wang, An Huang, Yifan Wang, Jiaying He, Fei Ling, Weihui Zhong
Summary: The asymmetric hydrogenation catalyzed by iridium/f-diaphos L1, L5 or L12 was successfully demonstrated for the first time, affording chiral alcohols with high conversions and moderate to excellent enantioselectivities. The protocol could be easily scaled up to gram-scale with a Turnover Number (TON) of 9700.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Shuailong Li, Dequan Zhang, Runtong Zhang, Shao-Tao Bai, Xumu Zhang
Summary: This article reports a novel rhodium catalyst that enables highly efficient and selective hydroformylation of cyclopropyl-functionalized trisubstituted alkenes, resulting in valuable chiral cyclopropyl entities. The modified ligand used in this study exhibits superior performance compared to traditional diphosphine ligands in asymmetric catalysis. Gram-scale reactions and subsequent transformations of the products were also demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Guiying Xiao, Chaochao Xie, Qianling Guo, Guofu Zi, Guohua Hou, Yuping Huang
Summary: A highly efficient asymmetric hydrogenation method has been developed for the synthesis of chiral gamma-hydroxy acid derivatives. The method shows excellent enantioselectivity and has the potential to be applied in the synthesis of chiral compounds and key intermediates for pharmaceutical synthesis.
Article
Chemistry, Physical
Vanessza Judit Kolcsar, Gyorgy Szollosi
Summary: This study focuses on developing a green system for the asymmetric transfer hydrogenation of ketones using chiral Ru catalyst in aqueous media and mechanochemical energy transmission. The scale-up of the system was successful with high yields of optically enriched alcohols. The developed mechanochemical system provides high TOFs up to 168 h(-1), making it a useful guide for the practical synthesis of optically pure chiral secondary alcohols.
Article
Chemistry, Multidisciplinary
Haibo Wu, Jianping Yang, Bram B. C. Peters, Luca Massaro, Jia Zheng, Pher G. Andersson
Summary: This study identified a single rhodium precursor that can achieve asymmetric full saturation of vinylarenes under both homogeneous and heterogeneous conditions. The asymmetric hydrogenation of styrenic olefins enabled by a ligand accelerated effect led to facial selectivity in consecutive arene hydrogenation. Tuning the ratio between phosphine ligand and rhodium precursor controlled the formation of catalytic species that operated without interference, showing potential for developing asymmetric arene hydrogenations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Heng Wang, Jialin Wen, Xumu Zhang
Summary: Asymmetric hydrogenation of double bonds is an effective method for preparing chiral molecules, with noble metals and bidentate ligands showing remarkable reactivity. The development of chiral tridentate ligands has become increasingly important, enabling both reactivities and stereoselectivities in asymmetric hydrogenation. While noble metal catalysts with chiral tridentate ligands have made significant achievements, there is still a high demand for designing chiral tridentate ligands for earth abundant metal catalysts.
Article
Chemistry, Multidisciplinary
Daiki Doiuchi, Tatsuya Nakamura, Hiroki Hayashi, Tatsuya Uchida
CHEMISTRY-AN ASIAN JOURNAL
(2020)
Review
Chemistry, Organic
Hiroki Hayashi, Tatsuya Uchida
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Hiroki Hayashi, Takamasa Ueno, Chungsik Kim, Tatsuya Uchida
Article
Chemistry, Organic
Masaki Yoshitake, Hiroki Hayashi, Tatsuya Uchida
Article
Chemistry, Organic
Daiki Doiuchi, Tatsuya Uchida
Summary: By reversible hydrolysis, the oxygen atom of water is activated to iodosylbenzene derivatives, serving as the oxygen source for ruthenium(bpga)-catalyzed site-selective C-H oxygenation. Sterically less bulky methinic and methylenic C-H bonds can be converted to desired oxygen functional groups in a site-selective manner. This method enables the preparation of oxygen-isotope labeled compounds on a multigram scale.
Article
Chemistry, Organic
Daiki Doiuchi, Tatsuya Uchida
Summary: This paper reviews recent developments in non-heme-type complex-catalyzed C-H oxidations over the last fourteen years, discussing the applications of site-selective, chemo-selective, diastereo-selective, and enantioselective transformations in C-H oxidations.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Sungho Nam, Ji Whan Kim, Hye Jin Bae, Yusuke Makida Maruyama, Daun Jeong, Joonghyuk Kim, Jong Soo Kim, Won-Joon Son, Hyein Jeong, Jaesang Lee, Soo-Ghang Ihn, Hyeonho Choi
Summary: In this study, a novel hyperfluorescent OLED was proposed, incorporating a Pt(II) complex as a phosphorescent sensitizer and a hydrocarbon-based and multiple resonance-based fluorophore as an emitter, which significantly improved the efficiency and lifetime of the device. The findings showed that using a multiple resonance-based fluorophore in OLEDs can lead to better understanding and higher performance.
Article
Chemistry, Multidisciplinary
Yushu Jin, Naoyuki Toriumi, Nobuharu Iwasawa
Summary: A highly efficient carboxylation method of benzyl alcohol derivatives with CO2 using a palladium/iridium dual catalyst under visible-light irradiation was developed. Site-selective carboxylation between benzylic C-O and aryl C-Cl moieties could be achieved simply by changing the palladium catalyst.
Article
Biochemistry & Molecular Biology
Yui Fujii, Makoto Yoritate, Kana Makino, Kazunobu Igawa, Daiki Takeda, Daiki Doiuchi, Katsuhiko Tomooka, Tatsuya Uchida, Go Hirai
Summary: Seven mono- and dihydroxycholesterols were synthesized by direct C-H oxidation of the cholestane skeleton using a Ru(Bpga) catalyst, which showed high selectivity for tertiary C-H. The reaction yielded a mixture of 25-, 20-, 17-, and 14-oxygenated cholesterols that could be easily separated by high-performance liquid chromatography. This suggests that late-stage C-H oxidation could be a viable strategy for preparing candidate metabolites of biologically important molecules.
Article
Multidisciplinary Sciences
Boobalan Ramadoss, Yushu Jin, Sobi Asako, Laurean Ilies
Summary: Regioselective functionalization of arenes is a challenging problem in organic synthesis. This study presents a strategy based on remote steric control, where a roof-like ligand protects the distant para site and enables selective activation of meta carbon-hydrogen (C-H) bonds.
Article
Chemistry, Organic
Yuki Yamakawa, Takashi Ikuta, Hiroki Hayashi, Keigo Hashimoto, Ryoma Fujii, Kyohei Kawashima, Seiji Mori, Tatsuya Uchida, Tsutomu Katsuki
Summary: C-H functionalization is a powerful tool for modifying bioactive compounds and creating new active molecules in late-stage transformations. However, its application is limited. This study demonstrates the efficient catalysis of an iridium-salen complex in asymmetric carbene C-H insertion reactions, achieving high stereoselectivity and regioselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Keisuke Tomohara, Nao Ohashi, Tatsuya Uchida, Takeru Nose
Summary: Plant extracts can be used as substrates for chemical engineering to synthesize artificial molecules with natural product-like structures. This method allows for efficient conversion in complex media and exhibits good selectivity and reproducibility. The study also discovered that some of the synthesized molecules exhibit promising inhibitory activity towards protease.
SCIENTIFIC REPORTS
(2022)
Article
Multidisciplinary Sciences
Yushu Jin, Joaquim Caner, Shintaro Nishikawa, Naoyuki Toriumi, Nobuharu Iwasawa
Summary: The authors report a rhodium-catalysed hydrocarboxylation of styrenes with CO2, using hydrogen as the terminal reductant. The carboxylation process is accelerated by visible light irradiation, and no additional base is required. The use of a cationic rhodium complex is critical for achieving high carboxylation selectivity.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Tatsuya Uchida
Summary: Direct C-H bond oxygenation is a strong and useful tool for constructing oxygen functional groups. The introduction of various non-heme-type iron and manganese complexes after pioneering work by Chen and White has led to significant developments in this field. However, to make this method truly useful in synthetic organic chemistry, further efforts are required to improve site-selectivity and catalyst durability.
Article
Chemistry, Physical
Young Mo Sung, Eun Suk Kwon, Yusuke Makida Maruyama, Youngsik Shin, Soo-Ghang Ihn, Jong Soo Kim, Hyeonho Choi, Hyo Sug Lee, Jung-Hwa Kim, Joonghyuk Kim, Soohwan Sul
Summary: Intramolecular charge transfer (ICT) and twisted intramolecular charge transfer (TICT) were studied in pyrene derivatives using time-resolved spectroscopy. The fluorescence behavior, including fluorescence intensity, was found to be solvent-dependent and can be modulated through structural modifications.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
