Article
Chemistry, Multidisciplinary
Guanghao Huang, Regis Guillot, Cyrille Kouklovsky, Boris Maryasin, Aurelien de la Torre
Summary: A broadly applicable diastereo- and enantioselective inverse-electron-demand Diels-Alder reaction of 2-pyrones and acyclic enol ethers is reported, leading to the synthesis of bridged bicyclic lactones with high yields and enantioselectivities using a copper(II)-BOX catalytic system. Mechanistic studies suggest a stepwise mechanism, and the synthetic potential of the bridged bicyclic lactones is demonstrated through the enantioselective synthesis of polyfunctional cyclohexenes and cyclohexadienes, as well as a carbasugar unit.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Byungjun Kim, Sukwoo Lee, Sarah Yunmi Lee
Summary: In this study, a new method was reported to successfully promote the catalytic asymmetric Diels-Alder reactions using a chiral catalyst in conjunction with a chiral isothiourea catalyst or a Bronsted acid, resulting in the synthesis of densely functionalized cyclohexenes with multiple stereocenters.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Organic
Soumik De, Aritra Kumar Dan, Raghaba Sahu, Debadutta Das
Summary: This review focuses on the role and mechanisms of various catalysts in synthesizing halocyclized products, highlighting the enantioselectivities, diastereoselectivities, and regioselectivities studied in existing literature.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Hiroto Uno, Koki Kawai, Taichi Araki, Motoo Shiro, Norio Shibata
Summary: Gem-difluoromethylene moieties are attractive in medicinal chemistry due to their ability to mimic other more ubiquitous functional groups. A novel asymmetric method for their construction was developed, allowing easy access to chiral 1,3-dioxanes that contain a tetrasubstituted difluoroalkyl stereogenic center. The gem-difluoro substitution pattern promotes the reaction, and various substrates were suitable for this method.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Ling-Fei Tao, Linghui Qian, Jia-Yu Liao
Summary: In this study, an unprecedented silver-catalyzed highly diastereo- and enantioselective [3+3] cycloaddition of activated isocyanides with azomethine imines was developed. This method features high efficiency, good to excellent stereocontrol, wide substrate scope, as well as operational simplicity. It is also noteworthy that the same catalytic system was proved to be suitable for not only the late-stage functionalization of complex bioactive molecules but also the kinetic resolution of racemic azomethine imines.
Article
Chemistry, Multidisciplinary
Mukulesh Mondal, Shubhanjan Mitra, Dylan J. Twardy, Manashi Panda, Kraig A. Wheeler, Nessan J. Kerrigan
Summary: This paper describes a versatile asymmetric synthesis of bicyclic pyrazolidinones through alkaloid-catalyzed formal [3+2]- and [3 + 2 + 2]-cycloadditions of ketenes with azomethine imines. The method shows good tolerance towards ketene and a variety of monosubstituted ketenes, with high yields and excellent diastereoselectivity and enantioselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Chiara Portolani, Giovanni Centonze, Sara Luciani, Andrea Pellegrini, Paolo Righi, Andrea Mazzanti, Alessia Ciogli, Andrea Sorato, Giorgio Bencivenni
Summary: The first catalytic enantioselective and diastereoselective synthesis of atropisomeric hydrazides was achieved using a sequential catalysis protocol, providing a stereodivergent approach to enantioenriched atropisomeric hydrazides. The resulting axially chiral hydrazides were obtained directly from commercially available reagents in high yields and with good stereocontrol, demonstrating the effectiveness of this strategy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Peng Zhang, Qi Xu, Xiao-Mei Wang, Jia Feng, Chuan-Jun Lu, Yingzi Li, Ren-Rong Liu
Summary: The first enantioselective synthesis of N-N bisindole atropisomers via palladium-catalyzed construction of one indole skeleton is reported in this study. A wide variety of N-N axially chiral bisindoles were generated with good yields and excellent enantioselectivities through a cascade condensation/N-arylation reaction. The reaction mechanism and enantiocontrol were further investigated using density functional theory (DFT) calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Ryotaro Yagita, Kazuhiro Irie, Chihiro Tsukano
Summary: In this study, the left-hand fragment of Schinortriterpenoids, a class of complex and highly oxygenated polycyclic terpenes, was successfully synthesized with excellent diastereoselectivity through [3+2] cycloaddition. Computational studies were used to investigate the stereoselectivity, and further selective transformations resulted in a tricyclic skeleton with the desired stereochemistry.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Joseph Benford-Ward, Sanaz Ahmadipour, Aliya Sembayeva, Louise Male, Richard S. Grainger
Summary: The synthesis of the naturally occurring (+)-dictyoxetane was achieved through catalytic asymmetric synthesis and the use of alternative methods. The study also investigated a range of related reactions to the synthesis target.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Niklas Rauscher, Line Noesborg, Christian Jandl, Thorsten Bach
Summary: In this study, the prezizane-type sesquiterpene agarozizanol B was synthesized through a photochemical cascade reaction, successfully achieving the key step of the synthesis with a specific strategy and obtaining the (+)-enantiomer that is identical to the natural product.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Inorganic & Nuclear
Macarena Corro, Oriol Salvado, Sara Gonzalez, Paula Dominguez-Molano, Elena Fernandez
Summary: The renaissance in the application of gem-diborylalkanes since 2010 has led to new synthetic applications towards C-C and C-N bond formation. Activation of gem-diborylalkanes by Cu(I) catalysts generates active borylalky copper(I) species, allowing efficient trapping of several electrophilic reagents. Furthermore, modification of Cu(I) complexes with chiral ligands induces asymmetric platforms for the synthesis of enantioenriched organoboron compounds.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Lulu Shen, Yin Zheng, Zitong Lin, Tianzhu Qin, Zhongxing Huang, Weiwei Zi
Summary: In this study, a binuclear copper-catalyzed method was developed to generate 2-aminoallyl cations from ethynyl methylene cyclic carbamates, which were then used for the enantioselective (3+2) cycloaddition reaction with indoles to construct chiral pyrroloindolines. This transformation exhibits a novel C1,N-dipolar reactivity for 2-aminoallyl cations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ken-Loon Choo, Bijan Mirabi, Karl Z. Demmans, Mark Lautens
Summary: Enantioenriched spiro-oxiranes with three contiguous stereocenters were synthesized using a rhodium-catalyzed cascade reaction, enabling the formation of a spirocyclic framework in a single step. Both sp(2)- and sp-hybridized carbon nucleophiles were found to be efficient initiators, yielding products with different functional groups. Derivatization studies demonstrated the synthetic versatility of the products' epoxide and alkyne moieties. DFT calculations were employed to explain spectroscopic discrepancies between solution- and solid-state structures of the products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Xiaohong Huo, Guanlin Li, Xi Wang, Wanbin Zhang
Summary: Bimetallic catalysis is an efficient strategy for developing new chemical reactions and stereodivergent synthesis, allowing for the preparation of products with different stereoisomers from the same set of starting materials.
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
Shuhei Akahori, Atsushi Kaga, Jinseok Kim, Hideki Yorimitsu, Dongho Kim, Hiroshi Shinokubo, Yoshihiro Miyake
Summary: In this study, C-4h-symmetric octaaza[8]circulenes were synthesized and exhibited enhanced antiaromaticity upon protonation. The protonation of the pyridine rings enhanced the contribution of the octaaza[8]circulenes' antiaromatic character.
CHEMISTRY-AN ASIAN 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
Multidisciplinary Sciences
Takayuki Itabashi, Kazuya Arashiba, Akihito Egi, Hiromasa Tanaka, Keita Sugiyama, Shun Suginome, Shogo Kuriyama, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: Dinitrogen is a valuable material for the synthesis of organonitrogen compounds. This study presents a catalytic reaction for the formation of cyanate anion from dinitrogen under ambient conditions. The use of molybdenum-PNP complexes as catalysts enables the synthesis of NCO- from dinitrogen in two steps.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Ken Sakata, Yuuri Uehara, Shiona Kohara, Takeshi Yoshikawa, Yoshiaki Nishibayashi
Summary: In this study, the effects of propargylic substituents on the enantioselectivity and reactivity in propargylic substitution reactions were further investigated using density functional theory calculations. The results showed that substitution of a methyl group at the propargylic position could reverse the stereoselectivity, while substitution of a trifluoromethyl group for a methyl group was suggested to enhance the enantioselectivity.
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)
Review
Chemistry, Inorganic & Nuclear
Yoshiaki Tanabe, Yoshiaki Nishibayashi
Summary: Recent studies summarize the use of transition metal-dinitrogen complexes for catalytic nitrogen fixation, with successful Mo catalytic systems and H2O as a proton source for NH3 formation. Future research plans aim to improve catalytic systems for increased efficiency.
COORDINATION CHEMISTRY REVIEWS
(2022)
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
Yuya Ashida, Yuto Onozuka, Kazuya Arashiba, Asuka Konomi, Hiromasa Tanaka, Shogo Kuriyama, Yasuomi Yamazaki, Kazunari Yoshizawa, Yoshiaki Nishibayashi
Summary: The development of a nitrogen fixation process that relies on renewable energy, such as visible light, is a goal in sustainable chemistry. In this study, the authors establish an iridium and molybdenum-catalysed process for synthesizing ammonia from dinitrogen under ambient reaction conditions and visible light irradiation.
NATURE COMMUNICATIONS
(2022)
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)
