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11.
Watanabe M Ikagawa A Wang H Murata K Ikariya T 《Journal of the American Chemical Society》2004,126(36):11148-11149
Well-defined chiral Ru amido complexes promoted asymmetric Michael addition of 1,3-dicarbonyl compounds including malonates, beta-keto esters, and 1,3-diketones to nitroalkenes to give the corresponding adducts with excellent ees and in excellent yields. 相似文献
12.
Kodera M Shimakoshi H Nishimura M Okawa H Iijima S Kano K 《Inorganic chemistry》1996,35(17):4967-4973
A mononucleating tripyridine ligand, 2-(bis(2-pyridyl)methyl)-6-methylpyridine (L(1)), and a dinucleating hexapyridine ligand, 1,2-bis[2-(bis(2-pyridyl)methyl)-6-pyridyl]ethane (L(2)), have been prepared. The reaction of a carbanion of 2,6-lutidine with 2-bromopyridine affords L(1) which is converted to L(2) quantitatively by treating with tert-butyllithium and 1,2-dibromoethane. (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) complexes [Fe(2)(O)(OAc)(2)(L(1))(2)](ClO(4))(2) (1) and [Fe(2)(O)(OAc)(2)L(2)](ClO(4))(2) (2) have been synthesized and characterized by means of infrared, UV/vis, mass, and M?ssbauer spectroscopies and by measuring magnetic susceptibility and cyclic voltammograms. All the spectral data are consistent with the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure in both 1 and 2. A relatively strong molecular ion peak at m/z 865 corresponding to [{Fe(2)O(OAc)(2)L(2)}(ClO(4))](+) in a FAB mass spectrum of 2 suggests the stabilization of the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure by L(2) in a solution state. The compound 2.DMF.2-PrOH.H(2)O, chemical formula C(44)Cl(2)Fe(2)H(51)N(7)O(16), crystallizes in the monoclinic space group C2/c with a = 22.034(6) ?, b = 12.595(5) ?, c = 20.651(7) ?, beta = 121.49(2) degrees, and Z = 4. The cation has 2-fold symmetry with the bridging oxygen atom on the 2-fold axis: Fe-(&mgr;-O) = 1.782(5) ?, Fe-O-Fe = 123.6(6) degrees, and Fe.Fe = 3.142(3) ?. The diiron(III) core structure of 2 seems to be stabilized by encapsulation of the ligand. Compound 2 is the first example of a discrete (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) complex with a dinucleating ligand. 相似文献
13.
Extremely Photostable Electron-Deficient Phthalocyanines that Generate High Levels of Singlet Oxygen
Prof. Dr. Taniyuki Furuyama Yusuke Miyaji Kazuya Maeda Prof. Dr. Hajime Maeda Prof. Dr. Masahito Segi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1678-1682
A robust lead-mediated synthetic procedure for the generation of phthalocyanines substituted with electron-withdrawing groups has been developed. The free-base phthalocyanine and various metal complexes were prepared without discernible degradation of the peripheral electron-withdrawing substituents. Upon irradiation with red light, some of the thus-obtained metal complexes generated high levels of singlet oxygen. In particular, a palladium complex exhibited attractive photostability upon exposure to singlet oxygen as a bleaching agent. The photostability of such complexes that may manifest concomitantly to the generation of high levels of singlet oxygen was attributed to the presence of the electron-withdrawing groups, which results in energetically low-lying highest occupied molecular orbitals. 相似文献
14.
Yoshino Katsurayama Prof. Yasuhiro Ikabata Prof. Hajime Maeda Prof. Masahito Segi Prof. Hiromi Nakai Prof. Taniyuki Furuyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(2):e202103223
The high penetration of near-infrared (NIR) light makes it effective for use in selective reactions under light-shielded conditions, such as in sealed reactors and deep tissues. Herein, we report the development of phthalocyanine catalysts directly activated by NIR light to transform small organic molecules. The desired photocatalytic properties were achieved in the phthalocyanines by introducing the appropriate peripheral substituents and central metal. These phthalocyanine photocatalysts promote cross-dehydrogenative-coupling (CDC) under irradiation with 810 nm NIR light. The choice of solvent is important, and a mixture of a reaction-accelerating (pyridine) and -decelerating (methanol) solvents was particularly effective. Moreover, we demonstrate photoreactions under visible-light-shielded conditions through the transmission of NIR light. A combined experimental and computational mechanistic analysis revealed that this NIR reaction does not involve a photoredox-type mechanism with electron transfer, but instead a singlet-oxygen-mediated mechanism with energy transfer. 相似文献
15.
Sun-Chan Jeong Ichiro Katayama Hirokane Kawakami Yutaka Watanabe Hironobu Ishiyama Nobuaki Imai Yoshikazu Hirayama Hiroari Miyatake Masao Sataka Hiroyuki Sugai Satoru Okayasu Shin-Ichi Ichikawa Katsuhisa Nishio Shinichi Mitsuoka Takamitsu Nakanoya Takashi Hashimoto Takanori Hashimoto Masahito Yahagi 《Solid State Ionics》2009,180(6-8):626-630
The diffusion coefficients of Li in the NaTl-type Li intermetallic compound of β-LiGa have been measured by using a short-lived radioactive diffusion tracer. As the tracer, the α-emitting radioisotope of 8Li delivered as the energetic and pulsed beam from Tokai Radioactive Ion Accelerator Complex (TRIAC) was implanted into the β-LiGa compounds with the composition in the range of about 43 to 54 at.% Li. By analyzing the time-dependent yields of the α-particles measured according to the repetition cycle of the beam, the tracer diffusion coefficients were extracted over the wide range of Li composition. Abnormal composition-dependence of Li diffusion coefficients in β-LiGa was observed; the stoichiometric β-LiGa showed the highest diffusivity of Li. By referring to the composition-dependent diffusivity of Li in the iso-structural β-LiAl and β-LiIn, we could identify the abnormal diffusion of Li in very Li-poor composition of β-LiGa. The anomaly has been discussed qualitatively in terms of the formation of defect complex and the interaction between the constitutional defects. 相似文献
16.
Masahito Segi Hiroaki Yamamoto Takeyoshi Hori Tadashi Nakajima 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):599-602
Selenoaldehydes and selenoketones, generated by thermal retro-Diels-Alder reaction of their cycloadducts with cyclopentadiene, reacted with oxygen-functionalized conjugated dienes such as 1-acetoxy-1,3-butadiene, Danishefsky's diene, and 1,4-diacetoxy-1,3-butadiene to give the corresponding cycloadducts in good yields regioselectively. 相似文献
17.
Masahito Sekiguchi Hiromichi Tanaka Noriaki Takami Akiya Ogawa Ilhyong Ryu Noboru Sonoda 《Heteroatom Chemistry》1991,2(3):427-430
The reduction of elemental selenium by samarium diiodide led to selective formation of selenolate anion species (Se2− and Se22−), the alkylation of which provided dialkyl selenides and diselenides, respectively, in excellent yields. 相似文献
18.
19.
20.
5-[4-(1-Hydroxyethyl)phenyl]-10,15,20-triphenylporphyrin (1a) and zinc porphyrin 1b were designed and synthesized to experimentally examine the validity of the transition-state model previously proposed for the lipase-catalyzed kinetic resolution of secondary alcohols. The lipases from Pseudomonas cepacia (lipase PS), Candida antarctica (CHIRAZYME L-2), Rhizomucor miehei (CHIRAZYME L-9), and Pseudomonas aeruginosa (lipase LIP) exhibited excellent enantioselectivity (E >100 at 30 degrees C). Subtilisin Carlsberg from Bacillus licheniformis (ChiroCLEC-BL) also showed high enantioselectivity for 1a (E = 140 at 30 degrees C), and the thermodynamic parameters were determined: DeltaDeltaH = -6.8 +/- 0.8 kcal mol(-1), DeltaDeltaS = -13 +/- 3 cal mol(-1) K(-1). Lipases and subtilisin showed R- and S-preference for 1, respectively. The mechanisms underlying the experimental observations are explained in terms of the transition-state models. The large secondary alcohol 1 is a powerful tool for investigating the conformation of the transition state of the enzyme-catalyzed reactions. The fact that 1 was resolved with high enantioselectivity strongly suggests that the gauche conformation, but not the anti conformation, is taken in the transition state, in agreement with the transition-state models involving the stereoelectronic effect. 相似文献