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Ruthenium‐Catalyzed Cycloisomerization of 2,2′‐Diethynyl‐ biphenyls Involving Cleavage of a Carbon–Carbon Triple Bond 下载免费PDF全文
Prof. Dr. Takanori Matsuda Kotaro Kato Tsuyoshi Goya Shingo Shimada Prof. Dr. Masahiro Murakami 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):1941-1943
A ruthenium complex catalyzes a new cycloisomerization reaction of 2,2′‐diethynylbiphenyls to form 9‐ethynylphenanthrenes, thereby cleaving the carbon–carbon triple bond of the original ethynyl group. A metal–vinylidene complex is generated from one of the two ethynyl groups, and its carbon–carbon double bond undergoes a [2+2] cycloaddition with the other ethynyl group to form a cyclobutene. The phenanthrene skeleton is constructed by the subsequent electrocyclic ring opening of the cyclobutene moiety. 相似文献
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Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage 下载免费PDF全文
Ze‐Kun Yang Dong‐Yu Wang Hiroki Minami Hiroyuki Ogawa Takashi Ozaki Dr. Tatsuo Saito Dr. Kazunori Miyamoto Dr. Chao Wang Prof. Dr. Masanobu Uchiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15693-15699
Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod)2] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh3)2Cl2] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot. 相似文献
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Joji Ohshita Takashi Kai Yohei Adachi Kosuke Yamaji Masashi Nakamura Seiji Watase Shingo Mori Noritsumi Matsuyama 《应用有机金属化学》2020,34(1):e5306
Disilane- and disiloxane-bridged bipyridyls ( DSBPy and DSOBPy ) were prepared and their optical properties were investigated in comparison with those of previously reported monosilane- and monogermane-bridged counterparts. The UV–visible absorption and photoluminescence bands of DSBPy and DSOBPy were blue-shifted as a result of elongation of the bridging units from monosilane and monogermane to disilane and disiloxane, likely due to the enhanced twisting of the bipyridyl units. Phosphorescent complexes DSBPy–Cu and DSOBPy–Cu were prepared by the interaction of DSBPy and DSOBPy with Cu2I2(PPh3)2. X-ray diffraction studies of their single-crystal structures revealed polymeric structures composed of repeat units of DSBPy or DSOBPy and [CuII(PPh3)]2. Organic light-emitting diodes with the ITO/PEDOT:PSS/ DSBPy–Cu or DSOBPy–Cu :PCTSQ/TAZ/Al structure were fabricated to examine the applications of the complexes as electroluminescent materials. The devices emitted yellow light with emission maxima at approximately 600 nm, and maximal luminance reached 120 and 190 cd m−2 for devices based on DSBPy–Cu and DSOBPy–Cu , respectively. The performance of the DSOBPy–Cu -based device was improved by using TAZ as the dopant of the emissive layer, and luminance was increased to 390 cd m−2. 相似文献
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Dr. Aya Yoshimura Yuki Takamachi Prof. Dr. Li‐Biao Han Prof. Dr. Akiya Ogawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):13930-13933
An efficient metal‐free diboration of terminal alkynes is reported. In the presence of a catalytic amount of organosulfides under light, the addition of bis(pinacolato)diboron (B2pin2) to terminal alkynes takes place efficiently to produce the corresponding double borylation products in good yields. Mechanistic studies indicate that this metal‐free sulfide‐catalyzed diboration of alkynes likely occurs by generation of a boryl‐centered radical with the aid of light and a sulfide, since such a radical was detected in the reaction mixture by electron spin resonance (ESR) spectroscopy. The present form of catalysis (sulfide/light) is thought to be unprecedented and provides a new means of preparation for organoboranes without heavy metal contamination in the products, which is highly desired in the preparation of drugs and electronic materials. 相似文献
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meso‐Dibenzoporphycene has a Large Bathochromic Shift and a Porphycene Framework with an Unusual cis Tautomeric Form 下载免费PDF全文
Dr. Koji Oohora Ayumu Ogawa Tamaki Fukuda Dr. Akira Onoda Prof. Dr. Jun‐ya Hasegawa Prof. Dr. Takashi Hayashi 《Angewandte Chemie (International ed. in English)》2015,54(21):6227-6230
meso‐Monobenzoporphycene (mMBPc) and meso‐dibenzoporphycene (mDBPc), in which one or two benzene moieties are fused at ethylene‐bridged positions (meso‐positions) of porphycene, were prepared in an effort to further delocalize the π‐electrons within the porphycene molecule. mMBPc and mDBPc were fully characterized by mass spectrometry, 1H and 13C NMR spectroscopy, and X‐ray crystallography. The longest‐wavelength Q‐bands of mMBPc and mDBPc are red‐shifted by 92 nm and 418 nm, respectively, compared to that of the unsubstituted porphycene (Pc). Electrochemical measurements indicate that the HOMO is destabilized and the LUMO is stabilized by the fused benzene moieties at the meso positions. Furthermore, both XPS and theoretical studies support the presence of a cis tautomeric form in the ground state of mDBPc, despite the fact that essentially all known porphycene derivatives adopt the trans tautomeric form. 相似文献
9.
Aya Yoshimura Akihiro Nomoto Mari Uchida Hiroki Kusano Tomokazu Saeki Akiya Ogawa 《Research on Chemical Intermediates》2017,43(6):3433-3443
The functionalization of polysilanes is an important subject in materials science because functionalized polysilanes are expected to exhibit potentially innovative properties. This research aims at the addition of a water-shedding property to polysilanes by introducing perfluoroalkyl groups into their skeleton. The photoinduced iodoperfluoroalkylation of various vinylsilanes takes place successfully upon irradiation with a xenon lamp: vinylmonosilanes undergo iodoperfluoroalkylation with perfluoroalkyl iodides (RfI) regioselectively, and the corresponding perfluoroalkylated silanes are obtained in moderate to high yields. Detailed optimization of the photoinduced iodoperfluoroalkylation has been investigated to apply this method to the functionalization of polysilanes. Polysilanes having vinyl groups can be synthesized by the reductive coupling of dichlorovinylsilanes with samarium diiodide (SmI2) and samarium metal (Sm) upon irradiation with visible light. The synthesized vinylpolysilanes and RfI (about 1.0 mM CHCl3 solution) are coated on a glass plate sequentially, and then the following photoirradiation with light of a wavelength over 300 nm successfully adds an excellent water-shedding property to the glass plate. 相似文献
10.
Yoshimasa Makita Tomofumi Danno Keisuke Ikeda Hsien-Han Lee Taro Abe Kento Sogawa Akihiro Nomoto Shin-ichi Fujiwara Akiya Ogawa 《Tetrahedron letters》2017,58(48):4507-4509
Hemicryptophanes are covalent molecular cages, constructed from a cyclotriveratrylene-based host unit and a functional unit linked by covalent spacers, which have been designed to accommodate endohedral functionalities in the cavity. In this study, the synthesis and characterization of the rigid, biphenyl-linked hemicryptophane 1 were investigated by NMR, ESI-MS, and X-ray crystallography. The structure of the inclusion complex, in which a dichloromethane molecule was constructed encapsulated within 1, was characterized by X-ray crystallography. An endohedral, cobalt(II) hemicryptophane complex 2 was also synthesized and characterized ESI-MS and X-ray crystallography. The X-ray crystal structure of 2 showed that the biphenyl-linked hemicryptophane had three components—a molecule each of chloroform and acetonitrile, and a cobalt(II) ion—within its cavity. 相似文献