Article
Chemistry, Multidisciplinary
Shiyao Liu, Yoshiaki Tanabe, Shogo Kuriyama, Ken Sakata, Yoshiaki Nishibayashi
Summary: In recent years, significant progress has been made in the development of transition metal-catalyzed enantioselective propargylic substitution reactions. However, until now, no successful example with phosphorus-centered nucleophiles has been reported. This study presents the first successful example of ruthenium-catalyzed enantioselective propargylic substitution reactions using propargylic alcohols as substrates and diarylphosphine oxides as phosphorus-centered nucleophiles, providing a new method for preparing chiral phosphorus-containing organic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Ling Li, Xiu-Shuai Chen, Xiang-Ping Hu
Summary: In this study, an intramolecular Cu-catalyzed asymmetric propargylic [4 + 2] cycloaddition reaction was achieved using a chiral tridentate N-ligand as the catalyst, leading to chiral tetrahydroisoindolo[2,1-a]quinoxalines with high yields and good to excellent enantioselectivities. The reaction is efficient, simple, and has a broad substrate scope, providing a powerful and concise strategy for the stereoselective synthesis of optically active polycyclic heterocycle frameworks.
Article
Chemistry, Organic
Si-Si Ning, Dan Meng, Jie-Yun Zhang, Shi-Lei Liu, Ni-Ni Zhou, Xiaojie Jin, Hai-Tao Zhu
Summary: A metal-free intramolecular [3+2] cycloaddtion of benzene-linked propynol-ynes in AcOH/H2O has provided a greener and more practical route to functionalized naphtho[1,2-c]furan-5-ones with high regioselectivity. Additionally, regioselective alpha-deuteration of the naphtho[1,2-c]furan-5-ones showed excellent deuterium incorporation and yields. The fluorescent properties of the naphtho[1,2-c]furan-5-one products were also investigated in solution.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Ruo-Qing Wang, Chong Shen, Xiang Cheng, Xiu-Qin Dong, Chun-Jiang Wang
Summary: In this study, copper-catalyzed asymmetric propargylic substitution was successfully achieved using salicylaldehyde-derived imine esters and propargylic carbonates, resulting in a wide range of chiral amino acid derivatives containing propargylic groups. The ortho-hydroxy group of the salicylaldehyde-derived imine esters played a crucial role in increasing reactivity and stabilizing the azomethine ylide.
CHEMICAL COMMUNICATIONS
(2022)
Article
Multidisciplinary Sciences
Xiang Pu, Qiu-Di Dang, Lei Yang, Xia Zhang, Dawen Niu
Summary: The authors report a doubly-stereoconvergent, Cu/Mg-catalyzed asymmetric propargylic substitution reaction that can selectively construct products with vicinal congested stereocenters. This reaction uses readily available starting materials, environmentally friendly catalysts, and has a broad substrate scope.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Chunming Gui, Yuanyuan Peng, Yang Zhou, Yixuan Zheng, Haifeng Wang, Qiongjiao Yan, Hui Zhou, Wei Wang, Fen-Er Chen
Summary: This paper reports the copper-catalyzed asymmetric propargylic substitution reaction, which efficiently synthesizes multifunctionalized products bearing a terminal alkyne unit with good stereoselectivity. The products can also be easily derivatized into other potentially valuable organic compounds, showing great potential for pharmaceutical development.
Article
Chemistry, Multidisciplinary
Shiyao Liu, Yoshiaki Tanabe, Shogo Kuriyama, Ken Sakata, Yoshiaki Nishibayashi
Summary: In this study, propargylic substitution reactions using ruthenium and copper catalysis with N-monosubstituted hydrazones as ambident nucleophiles were investigated. It was found that N-monosubstituted hydrazones exhibited different reactivities depending on the catalytic system, resulting in either propargylic alkylated or aminated products. DFT calculations were used to study the reaction pathways and further transformation of the products yielded multisubstituted pyrazoles in good to high yields.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Editorial Material
Chemistry, Multidisciplinary
Shiyao Liu, Yoshiaki Tanabe, Shogo Kuriyama, Ken Sakata, Yoshiaki Nishibayashi
Summary: The cover of this issue features the research on the propargylic substitution reaction of propargylic alcohol with an N-monosubstituted hydrazone, where the nucleophilicity of the hydrazone is controlled by the choice of catalytic system. The full article can be accessed at 10.1002/chem.202103287.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Dandan Sun, Thayalan Rajeshkumar, Yifan Li, Jiaxin Xu, Runkai Chen, Zhaohua Wan, Zongchao Lv, Laurent Maron, Yi-Hung Chen
Summary: Transition-metal-catalyzed cross-coupling of propargylic electrophiles and Grignard reagents provides useful synthetic intermediates. However, few examples exist for the conversion of propargylic derivatives into propargyl compounds due to the challenging regioselectivity. We demonstrate a regioselective and stereospecific propargylation of Grignard reagents using LaCl3.2LiCl as a catalyst in the absence of a ligand.
Article
Chemistry, Organic
Jinping Yuan, Pankaj Jain, Jon C. Antilla
Summary: The catalytic asymmetric addition of beta,gamma-substituted allylboronates to aldehydes has been described, showing highly efficient and selective reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Yong You, Yan-Ping Zhang, Zhen-Hua Wang, Jian-Qiang Zhao, Jun-Qing Yin, Wei-Cheng Yuan
Summary: Copper-catalyzed decarboxylative reactions of propargylic cyclic carbonates/carbamates are an efficient way to construct various useful skeletons. The field has gained attention and made significant progress due to the reaction sites of propargylic cyclic carbonates/carbamates and the advantages of copper catalysis. This review addresses the achievements, mechanisms, synthetic applications, limitations, challenges, and opportunities in this field.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Qi-Qi Yan, Cheng-Kai Ruan, Yu-Qin Deng, Yu-Chuan Pu, Wen-Dao Chu, Cheng-Yu He, Quan-Zhong Liu
Summary: Cu-catalyzed asymmetric propargylation of acyclic imines with electron-neutral protecting groups was established, providing the corresponding homopropargyl amines in excellent yields and high enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Qi-Qi Yan, Cheng-Kai Ruan, Yu-Qin Deng, Yu-Chuan Pu, Wen-Dao Chu, Cheng-Yu He, Quan-Zhong Liu
Summary: Cu-catalyzed asymmetric propargylation of acyclic imines with electron-neutral protecting groups was established, providing the corresponding homopropargyl amines in excellent yields and high enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Shweta Rohilla, Sadhna Shah, Vinod K. K. Singh
Summary: A copper-(II)-P,N,N-ligand catalyzed propargylic [3 +2] cycloaddition approach has been developed for the synthesis of optically enriched dihydrofuro-[3,2-c]-coumarins. The reaction utilizes propargylic esters as C2-bis-electrophiles and 4-hydroxycoumarin derivatives as C,O-bis-nucleophiles. This method was also applied to 4-hydroxy-2-quinolinones and 4-hydroxythiocoumarins, leading to the synthesis of various dihydrofuro-[3,2-c]-coumarins and their analogues with high enantioselectivities in moderate to good yields.
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, Inorganic & Nuclear
Takayuki Itabashi, Kazuya Arashiba, Shogo Kuriyama, Yoshiaki Nishibayashi
Summary: The molybdenum-nitride complex is functionalized by reacting with various carbon-centered electrophiles, resulting in the formation of new imide and acylimide complexes through carbon-nitrogen bond formation. The PNP ligand acts as a non-innocent ligand in reactions with phenylisocyanate and diphenylketene, leading to the formation of ureate and acylimide complexes. The nitrogen molecule is converted into an organic amide mediated by the molybdenum-nitride complex during the hydrolysis of the molybdenum-acylimide complex.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Takayuki Itabashi, Kazuya Arashiba, Hiromasa Tanaka, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: The molybdenum-nitride complex reacts with pinacolborane and diphenylsilane to form the corresponding borylimide-hydride and silylimide-hydride complexes. DFT calculations support the proposed reaction pathway involving hydroboration as a key step to produce the borylamine.
Article
Chemistry, Multidisciplinary
Shogo Kuriyama, Takeru Kato, Hiromasa Tanaka, Asuka Konomi, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: This study reports the synthesis of square-planar iron(I)-dinitrogen complexes supported by specific ligands, which exhibit excellent nitrogen fixation activity by catalyzing the conversion of dinitrogen gas into ammonia and hydrazine at low temperatures. Additionally, anionic iron(0)-dinitrogen complexes, which play a crucial role in the catalytic reaction, are isolated and characterized.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Article
Chemistry, Multidisciplinary
Yuya Ashida, Akihito Egi, Kazuya Arashiba, Hiromasa Tanaka, Taichi Mitsumoto, Shogo Kuriyama, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: In this study, a series of new chromium-halide, -nitride, and -dinitrogen complexes bearing carbene- and phosphine-based PCP-type pincer ligands were prepared and found to be effective catalysts for the reduction of dinitrogen to ammonia and hydrazine under atmospheric pressure.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yulin Zhang, Yoshiaki Tanabe, Shogo Kuriyama, Yoshiaki Nishibayashi
Summary: Successful hydroalkylation reactions of terminal alkynes with 4-alkyl-1,4-dihydropyridines under visible light irradiation using dual photoredox and nickel catalysis have been achieved, leading to the formation of alkylated alkenes with good-to-high yields. The regioselectivity of the products was effectively controlled by choice of coordination ligands for nickel species.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Mayu Nishijo, Shiho Mori, Tsubasa Nishimura, Hiroshi Shinokubo, Yoshihiro Miyake
Summary: Post-functionalization of porphyrinoid catalysts provides a powerful tool for fine-tuning their electronic structure. The N-methylation of diazaporphyrin complexes effectively controls their electron deficiency, Lewis acidity, and catalytic activity.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Shogo Kuriyama, Shenglan Wei, Hiromasa Tanaka, Asuka Konomi, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: A series of cobalt(I)-dinitrogen complexes with specific ligands were synthesized and characterized. These complexes serve as highly efficient catalysts for the formation of silylamine from dinitrogen at ambient conditions, producing a significant amount of silylamine.
INORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Shogo Kuriyama, Shenglan Wei, Takeru Kato, Yoshiaki Nishibayashi
Summary: A series of manganese complexes with anionic pyrrole-based PNP-type pincer ligand and anionic benzene-based PCP-type pincer ligand were synthesized and evaluated for their reactivity towards ammonia and silylamine formation. The results showed that only stoichiometric amounts of ammonia and silylamine were produced, possibly due to the instability of manganese pincer complexes under reducing conditions.
Article
Chemistry, Multidisciplinary
Takahiro Sakurai, Yuya Hiraoka, Hisaaki Tanaka, Yoshihiro Miyake, Norihito Fukui, Hiroshi Shinokubo
Summary: Ni-II 3,7,13,17-tetrapyridyl-5,15-diazaporphyrin acts as a double tridentate ligand for Pd-II ions, leading to the formation of a pincer-type bispalladium complex. The bispalladium complex exhibits excellent electron accepting ability and reversible redox properties due to the coordination of the two cationic Pd-II centers to the meso-nitrogen atoms. One- and two-electron reduction species of the bispalladium complex have been isolated, characterized, and confirmed to have a 20 pi antiaromatic nature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Akira Yamamoto, Xueshi Liu, Kazuya Arashiba, Asuka Konomi, Hiromasa Tanaka, Kazunari Yoshizawa, Yoshiaki Nishibayashi, Hisao Yoshida
Summary: Selective reductive conversion of organic and inorganic compounds has been achieved using a combination of samarium(II) diiodide (SmI2) and water. In this study, we used in situ X-ray absorption spectroscopy to analyze the structure of the Sm2+-water complex in tetrahydrofuran (THF) in the presence of water. The results provide fundamental insights into the reactivity and chemoselectivity of the Sm2+-water complex system.
INORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Yulin Zhang, Yoshiaki Tanabe, Shogo Kuriyama, Ken Sakata, Yoshiaki Nishibayashi
Summary: Recently, transition metal-catalyzed enantioselective free radical substitution reactions have been recognized as convenient and important tools in synthetic chemistry. In this paper, we present a strategy to control enantioselective propargylic substitution reactions with alkyl radicals under photoredox conditions using a dual photoredox and diruthenium catalytic system. The successful example of transition metal-catalyzed enantioselective propargylic substitution reactions with free alkyl radicals is described.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Taichi Mitsumoto, Yuya Ashida, Kazuya Arashiba, Shogo Kuriyama, Akihito Egi, Hiromasa Tanaka, Kazunari Yoshizawa, Yoshiaki Nishibayashi
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Taichi Mitsumoto, Yuya Ashida, Kazuya Arashiba, Shogo Kuriyama, Akihito Egi, Hiromasa Tanaka, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: We have designed and synthesized a new molybdenum complex based on the bond dissociation free energies of N-H bonds in molybdenum-imide complexes with different substituted pyridine-based PNP-type pincer ligands. The complex exhibited excellent catalytic activity in the formation of ammonia from the reaction of dinitrogen with samarium diiodide and water under ambient conditions, with a significant improvement in catalytic performance compared to the unmodified complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Shun Suginome, Yoshiaki Nishibayashi
Summary: Organonitrogen compounds play a vital role in our lives, with ammonia serving as the primary nitrogen source. While ammonia is currently produced from dinitrogen and dihydrogen using the energy-intensive Haber-Bosch process, research into the direct synthesis of organonitrogen compounds from N2 using transition metal complexes is still in its early stages.
Article
Chemistry, Inorganic & Nuclear
Aya Eizawa, Kazuya Arashiba, Hiromasa Tanaka, Asuka Konomi, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: Dimolybdenum complexes bearing 3,3'''-(1,1':3',1'':3'',1'''-quaterphenylene)-bridged pyridine-based PNP-type pincer ligand were designed and prepared based on DFT calculations. These complexes serve as effective catalysts for the conversion of dinitrogen to ammonia under ambient reaction conditions, using samarium diiodide as a reductant and water as a proton source.
DALTON TRANSACTIONS
(2023)
