Article
Chemistry, Organic
Shaocong Shen, Zhijian Zong, Nan Sun, Baoxiang Hu, Zhenlu Shen, Xinquan Hu, Liqun Jin
Summary: A well-defined geometry-constrained tridentate NNN-cobalt complex was developed for regio- and stereoselective hydrosilylation of 1,3-diynes, tolerating a wide range of symmetrical and unsymmetrical substrates. The scale-up reaction demonstrated the practicality and efficiency of the developed strategy for the synthesis of diverse 1,3-enynylsilanes.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Kosuke Takahashi, Steven J. Geib, Katsuhiro Maeda, Dennis P. Curran, Tsuyoshi Taniguchi
Summary: Monohydroboration of substituted 1,3-diynes with an N-heterocyclic carbene borane occurs under radical conditions using an azo initiator and a thiol as a polarity-reversal catalyst, providing stable NHC-(E)-alkynylalkenylboranes.
Article
Chemistry, Physical
Yin Xu, Gan-Lu Qian, Da-Qiu Cui, Peng-Cheng Qian, Chao-Yue Zhao, Xin Hong, Bo Zhou, Long-Wu Ye
Summary: Herein, a chiral Bronsted acid-catalyzed desymmetrization reaction of diynes is reported, providing a facile access to enantioenriched 1,3-diaminopropanol derivatives and γ-butyrolactones with high enantioselectivities. These products can be used as precursors for the synthesis of versatile N- and O-heterocycles, which are important structural cores of bioactive molecules. Control experiments and theoretical calculations are used to confirm the mechanism and elucidate the origin of enantioinduction.
Article
Chemistry, Organic
Tao Lei, Danyang Wan, Jingbo Lan, Yudong Yang
Summary: This study presents a catalytic oxidative C-H annulation of thiophenol derivatives with 1,3-diynes, offering an efficient synthetic approach to symmetrical and nonsymmetrical 3,3'-bibenzothiophenes. The protocol demonstrates a wide substrate scope, excellent functional group tolerance, high regioselectivity, and catalyst-enabled switchable mono/diannulation selectivity. Furthermore, three novel helical-type bithiophene heptagonal imides, potentially applicable in optoelectronic materials, are constructed based on this reaction.
Article
Chemistry, Organic
Ariel L. Burgio, Nicklas W. Buchbinder, Webster L. Santos
Summary: A facile method for the synthesis of (Z)-1,3-enynes is achieved through sequential copper-catalyzed regio- and stereoselective borylation-protodeboronation of 1,3-diynes. Pinacolborane, copper(II) acetate, and Xantphos are utilized as the ligand to efficiently introduce hydrogen and Bpin in a cis fashion, followed by rapid hydrolysis with water. The reaction exhibits wide substrate scope and proceeds in a chemoselective manner.
Article
Chemistry, Organic
Sheng Zhang, Hao Zhang, Zhuang-Ping Zhan
Summary: A highly efficient hydroallylation reaction of 1,3-diynes with allylborons was developed, with the regioselectivity governed primarily by the appropriate choice of the metal. A series of unsymmetrical and symmetrical 1,3-diynes could undergo this transformation leading to the switch of two regioselective allyl-functionalized 1,3-enynes when palladium and nickel bearing easily available phosphorus ligands were respectively employed.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Analytical
Mehmet Oguz, Serkan Erdemir, Sait Malkondu
Summary: This article introduces a ratiometric fluorescent probe based on the ICT mechanism for detecting hydrazine. The probe exhibits high sensitivity and selectivity, with the ability to detect hydrazine within approximately 2.0 minutes. Additionally, the probe demonstrates solvatochromism, indicating a high sensitivity to medium polarity. By constructing a portable smartphone platform, the probe is successfully applied to water samples, bioimaging, and environmental monitoring, suggesting significant potential applications.
ANALYTICA CHIMICA ACTA
(2022)
Article
Chemistry, Multidisciplinary
Katsuki Tanaka, Daisuke Sakamaki, Hideki Fujiwara
Summary: 5,12-Dihydro-5,12-diazatetracene (DHDAT) dimers with different substitution patterns were synthesized, revealing differences in electronic ground-state interaction, emission behavior, and thermochromic properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Lin-Jun Qi, Cui-Ting Li, Zheng-Qi Huang, Jia-Tian Jiang, Xin-Qi Zhu, Xin Lu, Long-Wu Ye
Summary: The study presents a novel copper-catalyzed asymmetric formal annulation reaction, which can synthesize a range of chiral oxygen-heterocycles via carbonyl ylides with excellent enantioselectivity and yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Spectroscopy
Felix Y. Telegin, Yuriy S. Marfin
Summary: A simple semiempiric phenomenological approach is developed to quantify the solvent effect on the absorption and emission properties of BODIPYs, based on a new rule describing the linear relationship between the difference and sum of absorption and emission wavenumbers. The approach demonstrates high reliability and advantages compared to traditional methods for analyzing solvatochromism in selected BODIPYs.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2021)
Article
Chemistry, Analytical
Serkan Erdemir, Sait Malkondu
Summary: Environment-sensitive fluorescent dyes have become important tools in fluorescence detection and imaging, particularly for polarity-responsive sensors. The novel isophorone and phenylamine dye (IPA) demonstrated recognition ability for Al3+ and solvatofluorchromic properties in various organic solvents. The dye’s turn-on NIR emissive and colorimetric response towards Al3+ was significant, and it could successfully determine water content in commercial alcoholic solutions.
MICROCHEMICAL JOURNAL
(2021)
Article
Chemistry, Organic
Sanjeev Kumar, Saiprasad Nunewar, Tharun Kumar Sabbi, Vinaykumar Kanchupalli
Summary: Here, we report the Rh(III)-catalyzed C-H activation followed by redox-neutral [3 + 2] annulation of sulfoxonium ylides with 1,3-diynes, delivering alkynated indenone derivatives. This method shows a broad substrate scope, good functional group tolerance, and mild reaction conditions.
Article
Chemistry, Organic
Jakub Szyling, Aleksandra Szymanska, Adrian Franczyk, Jedrzej Walkowiak
Summary: A simple, efficient, and selective method for the preparation of boryl-functionalized enynes or dienes via catalytic diboration has been developed. The method was proven to be effective and was applied in advanced organic transformations.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yi Luo, Lin Dong
Summary: An efficient synthetic method has been developed for the functionalization of bisindoles and indoles through catalyst-controlled C-H functionalization of pyrazolidinones and 1,3-diynes, providing a straightforward pathway with high selectivity for both chemoselectivity and regioselectivity challenges.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Mamoru Ito, Hideaki Onoda, Asahi Takaki, Takanori Shibata
Summary: We describe the synthesis of two nitrogen-containing polycyclic systems using gold-catalyzed cycloisomerizations. By choosing different substrates and coordinating ligands, it is possible to access different structures in a single reaction, showcasing the potential of gold-catalyzed reactions in the synthesis of polycyclic compounds.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Eisuke Sato, Gaku Tachiwaki, Mayu Fujii, Koichi Mitsudo, Takashi Washio, Shinobu Takizawa, Seiji Suga
Summary: The use of a flow reactor in electrolysis allows for efficient and scalable synthesis, which is typically challenging with batch reactors. We successfully achieved electrochemical carbon-Ferrier rearrangement using catalytic anodic oxidation in an electrochemical flow reactor. Gaussian process regression (GPR), a machine learning method, enabled the adjustment of numerical parameters derived from the flow reactor. GPR also facilitated the construction of two models for estimating yields and productivity, allowing for rational selection of reaction conditions.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Chemistry, Multidisciplinary
Tiancheng Tan, Tomoya Nakamura, Richard Murdey, Shuaifeng Hu, Minh Anh Truong, Atsushi Wakamiya
Summary: New near-infrared dyes combining BAr2-bridged azafulvene dimer acceptors with diarylaminothienyl donors were synthesized. Surprisingly, the azafulvene acceptor in these dyes adopted a 5-membered ring structure. The influence of aryl substituents on the energy levels of the dye compounds was evaluated through electrochemical and optical measurements.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Takafumi Shiraogawa, Jun-ya Hasegawa
Summary: Inverse molecular design is a promising method for optimizing molecules in chemical space and accelerating the development of functional materials. This work presents a new inverse design method based on quantum alchemy, which allows for efficient molecular design without empirical data. The method is demonstrated in the optimization of properties such as electric dipole moment and atomization energy in small chemical spaces. The results show faster convergence and lower computational cost using the proposed optimization scheme.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Organic
Koichi Mitsudo, Yasuyuki Okumura, Kotaro Yohena, Yuji Kurimoto, Eisuke Sato, Seiji Suga
Summary: Electrochemical dehydrogenative C-O bond formation was achieved for the synthesis of sultones. In the presence of K2CO3 and H2O, constant current electrolysis of [1,1'-biphenyl]-2-sulfonyl chloride resulted in quantitative formation of aryl-fused sultone. Control experiments suggest that electrochemical oxidation of sulfonates generates sulfo radical intermediates.
Article
Chemistry, Organic
Koichi Mitsudo, Keisuke Shigemori, Taro Shibata, Hiroki Mandai, Eisuke Sato, Seiji Suga
Summary: An electrochemical cross-coupling reaction between arylboronic esters and aryllithiums was developed, with the essential role of Br- in the electrolyte. NaBr was chosen as the electrolyte for its inexpensiveness and abundance, serving as a halogen mediator. Under mild conditions, the reaction yielded biaryls.
SYNTHESIS-STUTTGART
(2023)
Article
Nanoscience & Nanotechnology
Wentao Liu, Shuaifeng Hu, Jorge Pascual, Kyohei Nakano, Richard Murdey, Keisuke Tajima, Atsushi Wakamiya
Summary: The power conversion efficiency of tin-based halide perovskite solar cells is limited by the energy-level offset between the perovskite and conventional electron transport material. The use of ICBA as an alternative material shows promise due to its better energy level matching with tin-based perovskites. By optimizing the choice of solvent and annealing temperature, ICBA films with improved morphology and electrical properties are fabricated. These films exhibit reduced energy disorder and result in solar cells with high open-circuit voltages and conversion efficiencies. This research highlights the importance of controlling electron transport material properties and demonstrates the potential of solvent engineering for efficient device processing.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Inorganic & Nuclear
Kento Iwai, Yoshiyuki Mizuhata, Tomoya Nakamura, Masato Goto, Atsushi Wakamiya, Yuichi Shimakawa, Norihiro Tokitoh
Summary: Zwitterionic triarylmethylium dyes 1 and 2 with varied molecular assembly and charge transfer transition were synthesized using a tetraarylborate unit. These dyes exhibited solvatochromism and mechanochromism, allowing the color of the solid state to change upon dissolution & evaporation or grinding. Different crystal forms obtained from different recrystallization conditions independently reproduced the three colors, which were correlated with solid-state structures as demonstrated by diffuse reflectance measurement and powder X-ray diffraction. The unique color change of these dyes is suggested to originate from alterations in intermolecular interactions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Kai Oshiro, Min Gao, Lupeng Han, Dengsong Zhang, Jun-ya Hasegawa
Summary: In this study, the role of induced Fe and H2SO4 in preventing alkali poisoning was investigated. The results showed that Fe and H2SO4 can promote the formation of oxygen vacancies and generate characteristic adsorption sites, protecting NH3 adsorption sites on the catalyst surface from potassium poisoning. These findings are important for understanding the ability of metal oxide-based catalysts with sulfate ion against alkali poisoning and facilitating the tailored design of alkali tolerance catalysts.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Chika Higashimura, Go Yumoto, Takumi Yamada, Tomoya Nakamura, Fuyuki Harata, Hideki Hirori, Atsushi Wakamiya, Yoshihiko Kanemitsu
Summary: Two-dimensional halide perovskites exhibit unique structural and optical properties due to the distortion of the perovskite structure by large organic molecular cations, resulting in stable excitons confined in the 2D layers. In this study, the temperature dependences of various properties of a specific 2D perovskite crystal were investigated. The findings suggest that the anomalous temperature dependence of the Urbach tail parameter is caused by a random distribution of spontaneous polarizations in the ferroelectric phase.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Can Liu, Bang Lu, Hiroko Ariga-Miwa, Shohei Ogura, Takahiro Ozawa, Katsuyuki Fukutani, Min Gao, Jun-ya Hasegawa, Ken-ichi Shimizu, Kiyotaka Asakura, Satoru Takakusagi
Summary: In this study, the dynamic behavior of methoxy intermediate on a Pt/TiO2(110) surface during methanol decomposition has been investigated using STM, TPD, and DFT calculations. The results showed that the methoxy intermediates migrate on the TiO2 support surface to seek and find active Pt sites. This work provides a deeper understanding of the role of intermediate adsorbate migration in controlling the catalytic performance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Eisuke Sato, Ayaka Yukiue, Koichi Mitsudo, Seiji Suga
Summary: Anodic oxidation was used to achieve the aromatization of 1,2,3,4-tetrahydrocarbazoles. Nitrogen-protected tetrahydrocarbazoles were converted to carbazoles with the use of bromide as a mediator. The presence of AcOH and the inexpensive bromide source LiBr allowed for efficient transformation.
Article
Chemistry, Multidisciplinary
Takahiro Tsuchiya, Tomohiro Hamano, Masahiro Inoue, Tomoya Nakamura, Atsushi Wakamiya, Yasuhiro Mazaki
Summary: The introduction of diarylamino groups at the 2- and 6-positions of azulene leads to the reversal of the orbital energy levels and enables the HOMO-LUMO transition, resulting in a significant increase in absorbance in the visible region. Furthermore, the stability of their one-electron oxidized species is enhanced by introducing bromine or methoxy groups at the 1- and 3-positions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Takahiro Chiba, Kenji Iida, Shinya Furukawa, Jun-ya Hasegawa
Summary: The study investigates the effect of electric fields on hydrogen or proton transfer through hydroxyl groups on an anatase TiO2 (101) surface using first-principles density functional theory and the modern theory of polarization. Unidirectional surface proton transfer induced by external electric fields at different orientations towards the surface is the focus of this research. The preferred pathway for proton transfer can change depending on the magnitude and direction of the electric field. Detailed analysis reveals that the variation in the energy profile with the electric field is significantly different from the classical electric work of an electric field carrying a point charge. The electric field effect on the energy profile of proton transfer is governed by the rearrangement of the chemical bond network at the interface between water molecules and the surface.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Electrochemistry
Eisuke Sato, Mayu Fujii, Koichi Mitsudo, Seiji Suga
Summary: In this study, the alkynylation of aldehydes initiated by cathodic reduction was investigated. It was found that only a small amount of catalytic current was needed to completely consume the starting material. Cyclic voltammetry and control experiments suggested that the electron-generated base from the cathodic reduction of benzaldehyde promoted the alkynylation reaction.
Article
Chemistry, Multidisciplinary
Dragos Stoian, Toshiyuki Sugiyama, Atul Bansode, Francisco Medina, Wouter van Beek, Jun-ya Hasegawa, Akira Nakayama, Atsushi Urakawa
Summary: The surface intermediate species and oxygen vacancy-assisted mechanism over CeO2 catalyst in the direct dimethyl carbonate (DMC) synthesis have been investigated using transient spectroscopic methodologies and DFT-based molecular dynamics simulation. The results provide valuable insights into the reaction mechanism and explain the experimental observations.
