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51.
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
52.
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
53.
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
54.
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
55.
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
56.
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
57.
A previously proposed model describing the trapping site of the interstitial atomic hydrogen in borate glasses is analyzed. In this model the atomic hydrogen is stabilized at the centers of oxygen polygons belonging to B–O ring structures in the glass network by van der Waals forces. The previously reported atomic hydrogen isothermal decay experimental data are discussed in the light of this microscopic model. A coupled differential equation system of the observed decay kinetics was solved numerically using the Runge Kutta method. The experimental untrapping activation energy of 0.7×10−19 J is in good agreement with the calculated results of dispersion interaction between the stabilized atomic hydrogen and the neighboring oxygen atoms at the vertices of hexagonal ring structures. 相似文献
58.
Uchiyama N Matsunaga K Kiuchi F Honda G Tsubouchi A Nakajima-Shimada J Aoki T 《Chemical & pharmaceutical bulletin》2002,50(11):1514-1516
Trypanocidal constituents of dried leaves of Laurus nobilis L. (Lauraceae) were examined. Activity-guided fractionation of the methanol extract resulted in the isolation of two guaianolides, dehydrocostus lactone (1) and zaluzanin D (2), and a new p-menthane hydroperoxide, (1R,4S)-1-hydroperoxy-p-menth-2-en-8-ol acetate (3). The minimum lethal concentrations of these compounds against epimastigotes of Trypanosoma cruzi were 6.3, 2.5, and 1.4 microM, respectively. 相似文献
59.
Uchiyama C Shibata F 《Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics》1999,60(3):2636-2650
The method of projection operators, which plays an important role in the field of nonequilibrium statistical mechanics, has been established with the use of the Liouville-von Neumann equation for a density matrix to eliminate irrelevant information from a whole system. We formulate a unified and general projection operator method for dynamical variables. The main features of our formalism parallel those for the Liouville-von Neumann equation. (1) Two types of basic equations, time-convolution and time-convolutionless decompositions, are systematically obtained without specifying a projection operator. (2) Expansion formulas for both decompositions are also obtained. (3) Problems incorporating a time-dependent Liouville operator can be flexibly treated. We apply the formulas to problems in random frequency modulation and low field resonance. In conclusion, our formalism yields a more direct and easier means of determining the average time evolution of an operator than the one for the Liouville-von Neumann equation. 相似文献
60.
Sadao Takagi Mune Maeda 《Journal of inclusion phenomena and macrocyclic chemistry》1984,2(3-4):775-780
The enthalpies of transfer of cyclohexanol from aqueous to aqueous - or -cyclodextrin solutions have been measured at various mole fractions at 298.15 K on a rocking twin-microcalorimeter of heat-conduction type and the molar enthalpies, Gibbs energies, and entropies of inclusion in the aqueous solutions have been determined by the method proposed by the authors [Netsu Sokutei
10, 103 (1983)], to elucidate the driving force of the molecular inclusion. Discussions are given for all the systems obtained by the authors, concluding that the driving force is the enhancement of the entropy.Calorimetric studies on molecular inclusion V. 相似文献