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81.
Ning-Xin Xu Bi-Xiao Li Dr. Chao Wang Prof. Dr. Masanobu Uchiyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(26):10726-10731
Silicon-containing compounds are widely used as synthetic building blocks, functional materials, and bioactive reagents. In particular, silyl radicals are important intermediates for the synthesis and transformation of organosilicon compounds. Herein, we describe the first protocol for the generation of silyl radicals by photoinduced decarboxylation of silacarboxylic acids, which can be easily prepared in high yield on a gram scale and are very stable to air and moisture. Irradiation of silacarboxylic acids with blue LEDs (455 nm) in the presence of a commercially available photocatalyst releases silyl radicals, which can further react with various alkenes to give the corresponding silylated products in good-to-high yields with broad functional-group compatibility. This reaction proceeds in the presence of water, enabling efficient deuterosilylation of alkenes with D2O as the deuterium source. Germyl radicals were similarly obtained. 相似文献
82.
Suzuka Kinoshita Ryota Yamano Dr. Yu Shibata Yusuke Tanaka Kyoichi Hanada Dr. Takashi Matsumoto Prof. Dr. Kazunori Miyamoto Dr. Atsuya Muranaka Prof. Dr. Masanobu Uchiyama Prof. Dr. Ken Tanaka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):11113-11120
An S-shaped double helicene-like molecule (>99 % ee), possessing stable helical chirality, has been synthesized by the rhodium(I)/difluorphos complex-catalyzed highly diastereo- and enantioselective intramolecular double [2+2+2] cycloaddition of a 2-naphthol- and benzene-linked hexayne. The collision between two terminal naphthalene rings destabilizes the helical chirality of the S-shaped double helicene-like molecule, but the introduction of two additional fused benzene rings significantly increases the configurational stability. Thus, no epimerization and racemization were observed even at 100 °C. The enantiopure S-shaped double helicene-like molecule forms a trimer through the multiple C−H⋅⋅⋅π and C−H⋅⋅⋅O interactions in the solid-state. The trimers stack to form columnar packing structures, in which neighboring stacks have opposite dipole directions. The accumulation of helical structures in the same direction in the S-shaped double helicene-like molecule enhanced the chiroptical properties. 相似文献
83.
Masahiro Terashima Takuya Miyayama Tetsuro Shirao Hin Wai Mo Yasuhiro Hatae Hiroshi Fujimoto Katsumi Watanabe 《Surface and interface analysis : SIA》2020,52(12):948-952
Low-energy inverse photoelectron spectroscopy (LEIPS) and ultraviolet photoelectron spectroscopy (UPS) incorporated into the multitechnique XPS system were used to probe the ionization potential and the electron affinity of organic materials, respectively. By utilizing gas cluster ion beam (GCIB), in situ analyses and depth profiling of LEIPS and UPS were also demonstrated. The band structures of the 10-nm-thick buckminsterfullerene (C60) thin film on Au (100 nm)/indium tin oxide (100 nm)/glass substrate were successfully evaluated in depth direction. 相似文献
84.
Masaki Kondo Junichiro Kanazawa Tomohiro Ichikawa Takumi Shimokawa Yuki Nagashima Kazunori Miyamoto Masanobu Uchiyama 《Angewandte Chemie (International ed. in English)》2020,59(5):1970-1974
The silaboration of [1.1.1]propellane enables direct introduction of B and Si functional groups onto the bicyclo[1.1.1]pentane (BCP) scaffold in high yield under mild, additive‐free conditions. The silaborated BCP can be obtained on a gram‐scale in a single step without the need for column‐chromatographic purification, and is storable and easy to handle, providing a versatile synthetic intermediate for BCP derivatives. We also describe various conversions of the C?B/C?Si bonds on the BCP scaffold, including development of a modified Suzuki–Miyaura cross‐coupling reaction at the highly sterically hindered bridgehead sp3 carbon center of the BCP skeleton using a combination of highly activated BCP boronic esters, copper(I) oxide, and a PdCl2(dppf) catalyst system. 相似文献
85.
Hiroshi Takikawa Arata Nishii Hiromu Takiguchi Hirotoshi Yagishita Masato Tanaka Keiichi Hirano Masanobu Uchiyama Ken Ohmori Keisuke Suzuki 《Angewandte Chemie (International ed. in English)》2020,59(30):12440-12444
An intramolecular benzyne–phenolate [4+2] cycloaddition is reported. Benzyne precursors, having vicinal halogen‐sulfonate functionalities, linked with a phenol(ate) by various tether groups undergo efficient intramolecular [4+2] cycloaddition by treatment with either Ph3MgLi or nBuLi for halogen–metal exchange to form various benzobarrelenes. 相似文献
86.
Yulu Jiang Taro Ozaki Mei Harada Tadachika Miyasaka Hajime Sato Kazunori Miyamoto Junichiro Kanazawa Chengwei Liu Jun‐ichi Maruyama Masaatsu Adachi Atsuo Nakazaki Toshio Nishikawa Masanobu Uchiyama Atsushi Minami Hideaki Oikawa 《Angewandte Chemie (International ed. in English)》2020,59(41):17996-18002
Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome‐editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical‐induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue. 相似文献
87.
Yukiko Kamiya Fuminori Sato Keiji Murayama Atsuji Kodama Susumu Uchiyama Hiroyuki Asanuma 《化学:亚洲杂志》2020,15(8):1266-1271
Serinol nucleic acid (SNA) is a promising candidate for nucleic acid‐based molecular probes and drugs due to its high affinity for RNA. Our previous work revealed that incorporation of 2,6‐diaminpurine (D), which can form three hydrogen bonds with uracil, into SNA increases the melting temperature of SNA‐RNA duplexes. However, D incorporation into short self‐complementary regions of SNA promoted self‐dimerization and hindered hybridization with RNA. Here we synthesized a SNA monomer of 2‐thiouracil (sU), which was expected to inhibit base pairing with D by steric hindrance between sulfur and the amino group. To prepare the SNA containing D and sU in high yield, we customized the protecting groups on D and sU monomers that can be readily deprotected under acidic conditions. Incorporation of D and sU into SNA facilitated stable duplex formation with target RNA by suppressing the self‐hybridization of SNA and increasing the stability of the heteroduplex of SNA and its complementary RNA. Our results have important implications for the development of SNA‐based probes and nucleic acid drugs. 相似文献
88.
Yuzuru Uchida Katsumi Onoue Nobuaki Tada Fumio Nagao Hideaki Kozawa Shigeru Oae 《Heteroatom Chemistry》1990,1(4):295-306
Phosphine oxides bearing two or three 2-pyridyl groups react with organometallic reagents affording 2,2′-bipyridyl, 2-substituted pyridines and pyridine in good yields. Phosphonium salts and phosphine oxides, bearing at least two 2-pyridyl or substituted 2-pyridyl groups also give the corresponding 2,2′-bipyridyls and pyridines upon treatment with acid or neutral solvents such as water and alcohols in substantial yields. The 2,2′-bipyridyls are considered to be formed by ligand coupling within the pentacoordinated phosphorus intermediate formed incipiently during the reaction. 相似文献
89.
Hongyan Chen Rui Wang Miao Miao Xiaocan Liu Yonghui Ma Katsumi Hattori Peng Han 《Entropy (Basel, Switzerland)》2020,22(11)
In order to find out whether the geomagnetic storms and large-mega earthquakes are correlated or not, statistical studies based on Superposed Epoch Analysis (SEA), significance analysis, and Z test have been applied to the Dst index data and M ≥ 7.0 global earthquakes during 1957–2020. The results indicate that before M ≥ 7.0 global earthquakes, there are clearly higher probabilities of geomagnetic storms than after them. Geomagnetic storms are more likely to be related with shallow earthquakes rather than deep ones. Further statistical investigations of the results based on cumulative storm hours show consistency with those based on storm days, suggesting that the high probability of geomagnetic storms prior to large-mega earthquakes is significant and robust. Some possible mechanisms such as a reverse piezoelectric effect and/or electroosmotic flow are discussed to explain the statistical correlation. The result might open new perspectives in the complex process of earthquakes and the Lithosphere-Atmosphere-Ionosphere (LAI) coupling. 相似文献
90.
Wen Piao Satoru Tsuda Dr. Yuji Tanaka Dr. Satoshi Maeda Dr. Fengyi Liu Shodai Takahashi Yu Kushida Dr. Toru Komatsu Dr. Tasuku Ueno Dr. Takuya Terai Prof. Toru Nakazawa Prof. Masanobu Uchiyama Prof. Keiji Morokuma Prof. Tetsuo Nagano Dr. Kenjiro Hanaoka 《Angewandte Chemie (International ed. in English)》2013,52(49):13028-13032