Article
Chemistry, Multidisciplinary
Hasil Aman, Wei-Hua Chiu, Pin-Heng Liu, Gary Jing Chuang
Summary: An oxidative cleavage of alkenes catalyzed by 2,2-azobis(isobutyronitrile) with molecular oxygen as the oxidant was reported, yielding moderate amounts of carbonyl compounds and oxiranes under mild conditions. This study provided valuable insights into the mechanism of aerobic oxidative cleavage of alkenes.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Nanoscience & Nanotechnology
Debabrat Pathak, Rajiv Khatioda, Himanshu Sharma, Ankur K. Guha, Lakshi Saikia, Bipul Sarma
Summary: The oxidative cleavage of styrene C=C double bond was achieved using a nitrogen-rich triazine-based microporous organic polymer as an organocatalyst, leading to regioselective formation of benzaldehydes. This study highlights the potential applications of metal-free nitrogen-rich porous polymers in organic transformation reactions.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Tingting Li, Gerald B. Hammond, Bo Xu
Summary: A widely applicable approach to synthesize ketones, esters, and amides via the oxidative C-C bond cleavage of readily available alkyl aldehydes has been developed using green and abundant molecular oxygen as the oxidant, and base metals (cobalt and copper) as catalysts. This strategy can be extended to the one-pot synthesis of ketones from primary alcohols and alpha-ketoamides from aldehydes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Xuefeng He, Lina Zhang, Jiawei Chen, Huichong Liu, Yuming Su, Han Li, Yonghua Cao, Pavlo O. Dral, Cheng Wang
Summary: A photo-driven method using visible light is developed to selectively convert methane to methyl nitrates. This process involves a chlorine radical hydrogen atom-transfer cycle and nitration. The nitric acid is recyclable through hydrolysis and methanol can be obtained. Conversion of methane to liquid oxygenates is challenging but valuable.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yun-Yan Liang, Jing Huang, Xuan-Hui Ouyang, Jing-Hao Qin, Ren-Jie Song, Jin-Heng Li
Summary: This method allows for the facile synthesis of complex polyhaloalkanes through radical-mediated alkoxypolyhaloalkylation, and is well-suited for late-stage functionalization of complex molecules such as vitamin E, estrone, and cholesterol derivatives. The use of 4-methoxybenzenediazonium tetrafluoroborate as a radical initiator is crucial for the success of this transformation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ying Chen, Chao Chen, Yonghong Liu, Lei Yu
Summary: Catalyzed by cerium ammonium nitrate (CAN), the oxidative cracking reaction of alkenes occurred to produce carbonyls in good yields under mild conditions. The reaction employed molecular oxygen (O2) as the safe and clean oxidant. The catalyst dosage was reduced to as low as 0.5 mol%, while no additive was required. Thus, it may afford a generally green synthetic approach for introducing oxygen into organic molecules as well as the biomass degradation and the resource recycling from the C=C bond-containing waste polymers. X-ray photoelectron spectroscopy (XPS) analysis and control experiments demonstrated that the process proceeded via a single electron transfer (SET) reaction-initiated free radical reaction mechanism. In the process, both Ce and NO3- acted as the oxygen carrier to promote the oxidation reaction. The application of the abundantly existed nitrate in CAN was found to be the key for reducing the catalyst loading.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Chang-Cheng Wang, Guo-Xiang Zhang, Zhi-Wei Zuo, Rong Zeng, Dan-Dan Zhai, Feng Liu, Zhang-Jie Shi
Summary: A new chemical method has been developed to prepare benzoic acids and benzene polycarboxylic acids through the photo-induced oxidation of polyalkyl benzene, with CeCl3 as an efficient catalyst and dioxygen as the sole oxidant. This approach allows for the production of pure products from abundant petroleum feedstocks, offering advantages for large-scale implementation.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jieqing Wu, Jiwei Chen, Lei Wang, Hongjun Zhu, Rui Liu, Guangliang Song, Chao Feng, Yufeng Li
Summary: This study presents a Bronsted acid-promoted aerobic photo-oxygenation method for the efficient synthesis of aromatic acids and ketones. It eliminates the need for transition metal complexes or organic photosensitizers, which increases its potential for industrial applications.
Article
Chemistry, Applied
Jintao Wu, Zehui Peng, Tong Shen, Zhong-Quan Liu
Summary: In this study, a new method for the oxidative cleavage of C(2)=C(3)/C(2)-N bonds of indoles using electrochemistry as the driving force is reported. Compared to previous strategies, this method avoids the use of heavy metals or stoichiometric chemical oxidants, and features metal-free conditions, air as the oxidant, and easy scalability.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Palani Natarajan, Aleyna Basak, Onder Metin
Summary: A novel strategy for activating DMSO or DMSO-d(6) as a methylation agent was developed using a heterogeneous photo-Fenton-like method with gCN/MnO/MnO(OH) photocatalyst under visible light irradiation. The method showed practicality, cost-effectiveness, and low risk compared to conventional Fenton reagent systems. The gCN/MnO/MnO(OH) photocatalyst was easy to prepare, practical, economical, and could be reused without significant loss in its initial activity.
Article
Chemistry, Organic
Zhi-Cheng Yu, You Zhou, Xiang-Long Chen, Jin-Tian Ma, Li-Sheng Wang, Yan-Dong Wu, An-Xin Wu
Summary: A reductive coupling reaction was established for the synthesis of diaryl 1,2-dicarbonyl compounds from aryl methyl ketones. The reaction involves C(CO)-C(sp3) bond cleavage and proceeds through an electron transfer process. Notably, this reaction is simple to operate, has mild reaction conditions, and is applicable to a wide range of substrates.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Anupam Das, K. R. Justin Mohit, K. R. Justin Thomas
Summary: This study discovered a covalent organic framework that can cleave the (CC)-C-= bond of alkenes under light irradiation and convert them into their constituent carbonyl derivatives. The method is applicable for a wide range of alkenes and has high functional group tolerance and regioselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Shaohua Zhang, Shusong Liu, Yiying Sun, Shihao Li, Jiafu Shi, Zhongyi Jiang
Summary: Efficient chemical transformation is essential for modern society's sustainable development. Enzyme-photo-coupled catalytic systems (EPCS) show promise in solar-driven 'molecular editing', but the design of efficient and stable EPCS is challenged by the involvement of multiple components and catalytic processes. Identifying connectivity and compatibility between biocatalytic and photocatalytic ensembles as crucial factors governing EPCS performance, solutions for undesirable connectivity and low compatibility are discussed to propose designing principles for EPCS and provide a future perspective.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Organic
Yunlong Li, Haibo Liu, Zilong Huang, Yuan He, Bao-Hua Xu, Hongmei Wang, Zhengkun Yu
Summary: Functionalized 1,3-dienes were efficiently accessed through palladium-catalyzed Heck reaction under mild conditions, showcasing tolerance of various functional groups and further transformation potential to highly functionalized trisubstituted furan derivatives.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Organic
Yuan-Ye Jiang, Chao Chen
Summary: This review introduces the advances in computational studies on Cu-catalyzed aerobic reactions, focusing on the cooperation mechanisms of copper catalysts and O2 in dehydrogenation, oxygenation, and coupling reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Eri Sasaki, Yoshihiro Hayashi, Yuka Kimura, Sanae Sashida, Nobuhito Hamano, Kei Nirasawa, Keisuke Hamada, Fumihiko Katagiri, Yamato Kikkawa, Takaaki Sakai, Akihiro Yoshida, Masahiro Kawada, Shin-ichi Hirashima, Tsuyoshi Miura, Yoko Endo-Takahashi, Motoyoshi Nomizu, Yoichi Negishi
Summary: The study focused on developing A2G80-modified liposomes as a muscle-targeting nanocarrier for Duchenne muscular dystrophy (DMD) treatment. Through overlay assays, it was demonstrated that A2G80-LSP-Lip had an affinity for muscle tissue in mice and efficiently accumulated in muscle tissue when administered through the tail vein to DMD model mice. These results suggest that A2G80-LSP-Lip may serve as a useful tool for DMD treatment via systemic administration.
JOURNAL OF CONTROLLED RELEASE
(2021)
Article
Chemistry, Organic
Daiki Ishii, Shin-ichi Hirashima, Kosuke Nakashima, Hiroshi Akutsu, Takaaki Sakai, Yasuyuki Matsushima, Masahiro Kawada, Tsuyoshi Miura
Summary: A new organocatalyst efficiently promotes the asymmetric direct vinylogous conjugate additions of alpha-angelica lactones to benzoyl acrylonitrile derivatives, resulting in products with excellent enantioselectivities. The chiral gamma,gamma-disubstituted gamma-butenolides obtained can be readily transformed to valuable synthetic intermediates.
Article
Chemistry, Multidisciplinary
Kosuke Nakashima, Anton Petek, Yutaro Hori, Anton Georgiev, Shin-ichi Hirashima, Yasuyuki Matsushima, Dancho Yordanov, Tsuyoshi Miura, Liudmil Antonov
Summary: This study demonstrates the reimagined concept of long-range tautomeric proton transfer using crane subunits by designing and synthesizing two new acylhydrazones. The acylhydrazone subunits attached to the 7-OHQ act as crane arms for delivering protons to the quinoline nitrogen, providing different proton transport pathways with steric strain from the -CH3 group. Both compounds exhibit long thermal stability in the switched state, enabling tunable bidirectional proton cargo transport using different wavelengths of irradiation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Masahiro Kawada, Ryo Tsuyusaki, Kosuke Nakashima, Hiroshi Akutsu, Shin-ichi Hirashima, Takashi Matsumoto, Hikaru Yanai, Tsuyoshi Miura
Summary: The improved diaminomethylenemalononitrile organocatalyst facilitated enantioselective conjugate addition reaction of alpha-branched aldehydes with vinyl sulfone, resulting in adducts with excellent enantioselectivities (up to 96% ee). Mechanistic studies showed that the diaminomethylenemalononitrile motif interacts with the vinyl sulfone substrate using a single hydrogen bond and multiple weak interactions, including electrostatic C-H...O interactions.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Masahiro Kawada, Ryo Tsuyusaki, Kosuke Nakashima, Misaki Yamada, Akihiro Kozakai, Yasuyuki Matsushima, Shin-ichi Hirashima, Tsuyoshi Miura
Summary: This study presents the first successful example of asymmetric 1,2-additions of nitromethane to trifluoromethyl enones, and achieved highly functionalized products with high yields and excellent enantioselectivities through a novel N,N-dibenzyl diaminomethylenemalononitrile organocatalyst.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Review
Pharmacology & Pharmacy
Shin-ichi Hirashima
Summary: Organocatalysts have gained attention for being efficient and clean catalysts compared to metal catalysis. This article reviews the development of novel organocatalysts and their applications in reactions, focusing on push-pull ethylene moiety and diaminomethylenemalononitrile (DMM) organocatalysts. The study also includes the design and synthesis of novel organocatalysts with multiple hydrogen bond donors for asymmetric reactions.
YAKUGAKU ZASSHI-JOURNAL OF THE PHARMACEUTICAL SOCIETY OF JAPAN
(2021)
Article
Chemistry, Organic
Kosuke Nakashima, Anton Georgiev, Dancho Yordanov, Yasuyuki Matsushima, Shin-ichi Hirashima, Tsuyoshi Miura, Liudmil Antonov
Summary: The ability of long-range proton transport by the substitution of 7-hydroxyquinoline with sulfonamide and sulfonylhydrazone rotor units as a crane-arm has been studied. Different proton transport pathways triggered by different stimuli have been established based on the structure of the crane-arms. These compounds show solvent-driven proton switching, photoinduced long-range proton transport, and acid-triggered switching.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yasuyuki Matsushima, Yuta Iino, Yuka Tsuruta, Kosuke Nakashima, Shin-ichi Hirashima, Tsuyoshi Miura
Summary: The diaminomethylenemalononitrile organocatalyst efficiently facilitated the asymmetric conjugate addition-cyclization of cyclohexane-1,2-dione with benzylidenemalononitriles, leading to the formation of 2-amino-8-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitriles with high yields and excellent enantioselectivities (up to 90% ee). The use of this novel organocatalyst demonstrated improved enantioselectivities compared to previous reports.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Organic
Kosuke Nakashima, Asako Minai, Yuichi Okuaki, Yasuyuki Matsushima, Shin-ichi Hirashima, Tsuyoshi Miura
Summary: A novel squaramide organocatalyst efficiently promoted the asymmetric Friedel-Crafts alkylation of oc,6-unsaturated trifluoromethyl ketones with aromatic alcohols, affording the corresponding 6-trifluoromethyl-substituted 7,8-dihydrochromen-6-ol derivatives in high yields and enantioselectivity.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Organic
Daiki Ishii, Shin-ichi Hirashima, Hiroshi Akutsu, Kosuke Nakashima, Yasuyuki Matsushima, Takaaki Sakai, Tsuyoshi Miura
Summary: This study demonstrates the successful stereoselective conjugate addition using (Z)-benzoyl acrylonitriles and achieving excellent enantioselectivities.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Shin-ichi Hirashima, Eiki Hirota, Yasuyuki Matsushima, Naoki Noda, Yuya Nishimura, Takefumi Narushima, Kosuke Nakashima, Tsuyoshi Miura
Summary: This study presents an efficient organocatalytic method for the enantioselective hydrophosphinylation of various phosphine sulfides with aromatic and aliphatic nitroalkenes, resulting in chiral 13-nitrophosphine sulfides with high yields and enantioselectivities. Furthermore, the chiral beta-nitrophosphine sulfides can be easily converted into useful P, N-ligands and phosphine catalysts.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Organic
Kosuke Nakashima, Sumire Hanamura, Aoi Imamura, Yasuyuki Matsushima, Shin-ichi Hirashima, Tsuyoshi Miura
Summary: This study investigates the asymmetric Friedel-Crafts alkylation of indoles with alpha,beta-unsaturated trifluoromethyl ketones using a squaramide organocatalyst. The squaramide organocatalyst efficiently promotes the reaction, yielding products with both indole motif and trifluoromethyl group in high yields and excellent enantioselectivities (up to 99% ee). The transformation of the obtained adduct to a chiral spiro indoline 3-one is also demonstrated.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Ryo Tsuyusaki, Kosuke Nakashima, Miki Shimomura, Masahiro Kawada, Yasuyuki Matsushima, Shin-ichi Hirashima, Tsuyoshi Miura
Summary: An organocatalyst derived from quinine efficiently promoted the asymmetric Henry reaction between a,b-unsaturated trifluoromethyl ketones and nitromethane, resulting in highly functionalized products with excellent yields and high enantioselectivities (up to 94% ee).
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Yasuyuki Matsushima, Shunsuke Fukuda, Yusuke Kobayashi, Hiroyasu Nezu, Kosuke Nakashima, Shin-ichi Hirashima, Tsuyoshi Miura
Summary: High yields and excellent enantioselectivities (up to 92% ee) of phthalide derivatives were achieved by using a N,N-dibenzyl diaminomethylenemalononitrile organocatalyst in the asymmetric 5-exo bromolactonization of stilbene-type carboxylic acids. This is the first report demonstrating the successful synthesis of highly optically pure phthalide derivatives as the main product using the asymmetric 5-exo bromolactonization of stilbene-type carboxylic acids with various substituents.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Daiki Ishii, Shin-ichi Hirashima, Kosuke Nakashima, Yasuyuki Matsushima, Takaaki Sakai, Hiroshi Akutsu, Tsuyoshi Miura
Summary: This study demonstrates for the first time the efficient promotion of asymmetric direct vinylogous conjugate addition of alpha,beta-unsaturated gamma-butyrolactam to benzoyl acrylonitriles using thiourea organocatalyst, resulting in the formation of addition products with good yields and excellent stereoselectivities (up to 99% ee).
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
