Article
Chemistry, Organic
Cunzhi Chen, Shuyan Fang, Mingwu Yu, Jiaxi Xu, Zhanhui Yang
Summary: In this study, tetrasubstituted thiophenes were produced in a redox-neutral manner through site-specific and regio-selective transannulation of Allenoates with 1,2,3-thiadiazoles in the presence of catalytic Rh(i)/bisphosphine. The 1,2,3-thiadiazoles act as masked 1,3-dipoles with nucleophilic sulfur and electrophilic carbon termini.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Hannah S. Slocumb, Shaozhen Nie, Vy M. Dong, Xiao-Hui Yang
Summary: This study demonstrates the first enantioselective hydroselenation of styrenes, accessing organoselenium building blocks with selectivity for the branched isomer. Through a Rh-hydride pathway, C-Se bonds can be formed with excellent regio- and enantiocontrol.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Melissa Ramirez, Dennis Svatunek, Fang Liu, Neil K. Garg, Kendall N. Houk
Summary: The Diels-Alder reactions of furans and pyrroles with 1,2-cyclohexadiene and oxa- and azaheterocyclic analogs exhibit endo selectivity, which is determined by the interaction of molecular orbitals and electrostatic effects. This selectivity, based on stabilizing interactions, is expected to lead to the increased use of strained cyclic allenes in chemical synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Weiwei Chai, Qingyang Zhou, Wenna Ai, Yin Zheng, Tianzhu Qin, Xiufang Xu, Weiwei Zi
Summary: This study presents a novel method for the (3+2) cycloaddition reactions of palladium-oxyallyl species with 1,3-dienes, leading to the formation of five-membered carbocycles with C-C bond formation. The research also achieved regiodivergent access to cyclopentanones and cycloheptanones by tuning the steric properties of the palladium ligand. The reaction mechanism was investigated using DFT calculation, providing insights into the regioselectivities of the cycloaddition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Shabbir Ahmed Khan, A. Sanjeeva Kumar, K. C. Kumara Swamy
Summary: DBU-catalyzed spiro-annulation and ring expansion/dominoreaction of delta-acetoxy allenoates with cycl-2-ene-N-sulfonyl hydrazides led to ring-expanded products. On the other hand, cycl-3-ene/ane-N-sulfonyl hydrazones under similar conditions gave pyrazolecores. The key intermediates of spirocyclic and dienyl-amine were isolated and characterized. An extension to (R)-(-)-carvone-derived sulfonyl hydrazide also resulted in ring expansion and formation of pyrazoloazepine.
Article
Chemistry, Organic
Liam M. Joyce, Stephen A. Moggach, Christopher J. T. Hyland, Stephen G. Pyne, Scott G. Stewart
Summary: A nickel-catalyzed tetradehydro-Diels-Alder reaction of (E)-3-ene-1,8-diynes has been developed for the synthesis of isoindolines, dihydroisobenzofurans, and tetrahydroisoquinolines. Air-stable nickel catalysts, including novel nickel(0)-phosphite catalysts, were employed in this study. Additionally, the mechanism of trapping nickellacycle intermediates with pinacolborane to yield vinyl boronates was discussed to gain insights into the initial cycloisomerization process.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Christian L. L. Jankovic, Kyle C. C. McIntosh, Verner A. A. Lofstrand, F. G. West
Summary: Mild fluoride-mediated desilylative conditions generate 1,2-cyclohexadienes, which undergo efficient intramolecular [2+2] trapping to form tricyclic alkylidene cyclobutanes with complete diastereoselectivity for the cis-fused products. These cyclohexadienes can be trapped by pendent styrenes or electron-deficient olefins, and 14 substrates have been disclosed. The reactions achieve yields up to 91% at ambient temperature using only cesium fluoride and the necessary precursors are easily accessible from substituted 2-bromocyclohexenones.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Wanlong Xiao, Lichao Ning, Shuang Xin, Shunxi Dong, Xiaohua Liu, Xiaoming Feng
Summary: An efficient catalytic asymmetric [2+2] cycloaddition of allenyl imide and mono- or disubstituted alkenes has been developed. The use of chiral magnesium(II) complex of N,N'-dioxide allows for high yield and excellent enantioselectivity of axially chiral cyclobutenes and four-membered ring-containing spirocycles. This methodology can also be applied for the late-stage modification of biologically active molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Kwan Hong Min, Naeem Iqbal, Eun Jin Cho
Summary: By utilizing a rare bidentate primary aminophosphine ligand, a nickel-catalyzed reductive coupling of alkynes and amides was achieved, leading to the synthesis of highly functionalized indoles containing trifluoromethyl groups, which is of significance in drug research.
Article
Chemistry, Physical
Qianqian Lu, Jun Gu, Fang Liu, Chunsen Li
Summary: In this study, density functional theory calculations were used to investigate the influence of tethered unsaturated carbon-carbon bond on the cycloisomerization mechanisms in rhodium(I)-catalyzed reactions of 1,6-allenynes. The results showed that distinct regioselectivity between alkene and alkyne insertions and the contrasting reactivity of rhodium-alkyl and rhodium-alkenyl intermediates contribute to the divergent cycloisomerization mechanisms. Further analysis revealed the effects of alkyne substituent and carbon chain length of the reactant on product selectivity.
Article
Chemistry, Organic
Nuan Chen, Ting Zhou, Hong Zhang, Yuqi Zhu, Ming Lang, Jian Wang, Shiyong Peng
Summary: An unprecedented copper-catalyzed tandem reaction of 1,6-enynes with diazo compounds via a cross-coupling/[2 + 2] cycloaddition sequence was reported, leading to the synthesis of a library of methylenecyclobutane-fused ring systems with high proximal-regioselectivity and diastereoselectivity. Moreover, the key intermediate of 1,6-allenene proceeds via a thermally promoted [2 + 2] cycloaddition in the absence of copper catalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Carlos Lazaro-Milla, Pedro Almendros
Summary: This study presents a sustainable and efficient synthesis of new quinoline derivatives with one or two SO2CF3 groups, without the need for metal, catalyst, or irradiation. The method uses readily available and stable precursors, avoiding the formation of side products, while being able to tolerate a wide range of functional groups under mild conditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Jing Liu, Yi Zhou, Jiaqi Zhu, Zhi-Xiang Yu
Summary: The report describes a synthetic strategy for molecules with linear tricyclic 5/5/5 and 6/5/5 skeletons using a [5 + 2 + 1]/ene approach. The strategy involves a Rh-catalyzed [5 + 2 + 1] reaction followed by an InCl3-catalyzed ene reaction to transform the intermediates into the final target molecules, offering an efficient and feasible synthetic route.
Article
Chemistry, Multidisciplinary
Mehmet Arslan, Ozgur Ceylan, Rabia Arslan, Mehmet Atilla Tasdelen
Summary: This study focuses on the benign chemical modification of unsaturated polymers using UV-induced Paterno-Buchi [2 + 2] cycloaddition, resulting in the fabrication of organogels with tailorable crosslinking degrees and physical characteristics. The reactive double bonds in backbone chains of unsaturated polymers offer an easy way for structural modification, leading to outstanding elastic properties and high commercial availability of these materials.
Article
Chemistry, Multidisciplinary
Shang-Hai Yu, Tian-Jun Gong, Yao Fu
Summary: A cooperative Cu/Pd-catalysed borylallenylation of 2-trifluoromethyl-1,3-enynes with propargylic carbonates under mild reaction conditions was developed, providing facile and efficient access to conjugated bisallenes with a broad range of functional groups.
CHEMICAL COMMUNICATIONS
(2022)
Article
Biochemistry & Molecular Biology
Huili Lu, Shi-Wei Liu, Mengyang Li, Baocai Xu, Li Zhao, Tao Yang, Gao-Lei Hou
Summary: In this study, a novel ionic complex was systematically studied to investigate the stabilization of carbonic acid by bisulfate ion. It was found that bisulfate ion efficiently stabilized all three conformers of carbonic acid and reduced their energy differences compared to the isolated molecule. The complex showed good thermal stability at finite temperatures, and the hydrogen bonding properties and infrared spectra were also explored. This research is potentially important for understanding the fate of carbonic acid in complex environments.
Article
Chemistry, Multidisciplinary
Mengying Han, Shohei Tashiro, Takafumi Shiraogawa, Masahiro Ehara, Mitsuhiko Shionoya
Summary: This study reports a catalyst, porous metal-macrocycle framework (MMF), that can chemically activate Pd centers precisely for specific catalytic long-range olefin migration reactions. The reaction specificity is related to the arrangement mode of the Pd active centers in the confined space.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Article
Chemistry, Inorganic & Nuclear
Shuaifeng Hu, Pei Zhao, Bo Li, Pengwei Yu, Le Yang, Masahiro Ehara, Peng Jin, Takeshi Akasaka, Xing Lu
Summary: In this study, the crystallographic characterization of unprecedented erbium-based trimetallic clusterfullerenes was reported, revealing their exceptional electronic structure. The lifted bat ray configuration of the inner cluster was found to be associated with the bonding interactions between the inner metals, providing insights into the nature of metal-metal bonding.
INORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Zhen Lei, Mizuki Endo, Hitoshi Ube, Takafumi Shiraogawa, Pei Zhao, Koichi Nagata, Xiao-Li Pei, Tomoya Eguchi, Toshiaki Kamachi, Masahiro Ehara, Takeaki Ozawa, Mitsuhiko Shionoya
Summary: Photoluminescent gold clusters with unique chemical and physical properties based on the perturbed electronic structures have been synthesized using N-heterocyclic carbene ligands.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Yuan Shui, Gerui Pei, Pei Zhao, Mo Xiong, Sidian Li, Masahiro Ehara, Tao Yang
Summary: This study investigates the electronic structures, chemical bonding, and dynamic fluxionality behavior of endohedral metal-metal-bonding fullerenes through various bonding analysis methods. The results reveal the existence of a two-center two-electron sigma covalent bond between encapsulated metals inside fullerenes. Additionally, two covalent bonds are found between the metal dimer and fullerenes, leading to a covalent bonding nature between the metal dimer and fullerene cage. Furthermore, the dynamic fluxionality behavior of the metal dimer inside the fullerene is revealed, and the energy barrier for this behavior is analyzed.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Shuaifeng Hu, Pei Zhao, Kyohei Nakano, Robert D. J. Oliver, Jorge Pascual, Joel A. A. Smith, Takumi Yamada, Minh Anh Truong, Richard Murdey, Nobutaka Shioya, Takeshi Hasegawa, Masahiro Ehara, Michael B. B. Johnston, Keisuke Tajima, Yoshihiko Kanemitsu, Henry J. J. Snaith, Atsushi Wakamiya
Summary: In this study, it is found that the surface treatment of mixed tin-lead halide perovskite films with piperazine promotes charge extraction, and combined treatment with CPTA reduces hysteresis and improves efficiency and stability of solar cells.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Physical
Yutaka Maeda, Rina Morooka, Pei Zhao, Daiki Uchida, Yui Konno, Michio Yamada, Masahiro Ehara
Summary: The stepwise chemical functionalization of single-walled carbon nanotubes (SWNTs) was employed to selectively control site-specific functionalization and photoluminescence (PL). The addition site and the magnitude of the local band gap were found to be controlled by the steric hindrance of the added group and the R value in an (n,m) chiral nanotube.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Yui Konno, Rina Morooka, Tatsunari Morishita, Pei Zhao, Naoto Miyasaka, Kazuki Ono, Akira Noda, Daiki Uchida, Ren Iwasaki, Michio Yamada, Masahiro Ehara, Yutaka Maeda
Summary: Functionalization of single-walled carbon nanotubes (SWNTs) using a series of bromoalkanes and dibromoalkanes with different tether lengths was investigated. Longer tether lengths (six or more) resulted in SWNT adducts with two new photoluminescence (PL) peaks, while shorter tether lengths (3-5) produced single peaks. The formation mechanism of functionalized adducts was found to be influenced by the tether length, with shorter tethers tending to produce kinetic products.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Pei Zhao, Masahiro Ehara
Summary: This study systematically explored the activation of NO at metal/oxide interfaces using various metal oxide supports and platinum-group metal clusters. The Pt-4 and Rh-4 clusters showed stronger adsorption energies than the Pd-4 cluster, with the α-Al2O3(100) surface showing the lowest adsorption energy. The activation of NO was found to be an exothermic process, except for the Sr3Fe2O7 case, highlighting the importance of the interplay between the metal cluster and oxygen vacancy.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Leonardo Hayato Foianesi-Takeshige, Xiao-Li Pei, Pei Zhao, Hitoshi Ube, Zhen Lei, Masahiro Ehara, Mitsuhiko Shionoya
Summary: This study reports a carbon-centered gold cluster with reversible multi-stimuli responsiveness and reveals the relationship between its photophysical properties and ligand conformation through structural analysis and theoretical calculations. Additionally, the study finds that the gold cluster can emit green light even after losing crystallinity, which is a highly promising model compound for understanding the principles governing stimuli-responsiveness in metal clusters.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Yutaka Maeda, Yasuhiro Suzuki, Yui Konno, Pei Zhao, Nobuhiro Kikuchi, Michio Yamada, Masaya Mitsuishi, Anh T. N. Dao, Hitoshi Kasai, Masahiro Ehara
Summary: The authors achieved a shift in the photoluminescence wavelength of single-walled carbon nanotubes to 1320 nm by functionalizing them with 1,4-diiodooctafluorobutane. This finding contributes to the development and application of near-infrared light-emitting materials.
COMMUNICATIONS CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhen Lei, Pei Zhao, Xiao-Li Pei, Hitoshi Ube, Masahiro Ehara, Mitsuhiko Shionoya
Summary: The aim of this study is to metallize and control the photoluminescence properties of a carbon-centered hexagold(I) cluster using N-heterocyclic carbene (NHC) ligands and silver(I) ions. The results show that the photoluminescence of the clusters depends on the rigidity and coverage of the surface structure. Increasing the coverage of silver(I) ions enhances the phosphorescence efficiency.
Review
Chemistry, Multidisciplinary
Yutaka Maeda, Pei Zhao, Masahiro Ehara
Summary: This review summarizes the latest research progress in tailoring the near-infrared photoluminescent properties of single-walled carbon nanotubes through oxidation and alkylation. The emission wavelength of SWCNTs can be controlled in the range of 1100-1320 nm by chemical modification, and recent developments in chiral separation techniques have increased our understanding of the control of emission wavelength by chemical modification of SWCNTs with different chiral indices.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Yutaka Maeda, Rina Morooka, Pei Zhao, Michio Yamada, Masahiro Ehara
Summary: The chiral separation of functionalized SWNTs was achieved through thermal treatment, leading to a shift in emission radiation wavelength. This shift is attributed to the competition between rearrangement and elimination reactions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Takafumi Shiraogawa, Giulia Dall'Osto, Roberto Cammi, Masahiro Ehara, Stefano Corni
Summary: This study proposes an inverse design method for optimizing the molecule-nanoparticle system and incident electric field to achieve desired photophysical properties. The method utilizes a gradient-based optimization search within the time-dependent quantum chemical description for the molecule and the continuum model for the metal nanoparticle. The design results demonstrate the potential of the method for accelerating the discovery of efficient molecular plasmonics systems.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)