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11.
Prof. Dr. Azusa Kondoh Takayuki Hirozane Prof. Dr. Masahiro Terada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(42):e202201240
The formal enantioselective umpolung addition of dialkyl phosphites to 2-azaaryl ketones was developed under Brønsted base catalysis. The reaction involves the enantioselective protonation of the transient α-oxygenated (2-azaaryl)methyl anion generated through the 1,2-addition of the anion of dialkyl phosphite to the 2-azaaryl ketone and the subsequent [1,2]-phospha-Brook rearrangement. A chiral bis(guanidino)iminophosphorane organosuperbase efficiently catalyzed the reaction to provide enantio-enriched phosphates in high yields with good to high enantioselectivities. This is a rare example of the catalytic enantioselective protonation of transient carbanions other than enolates, constructing a trisubstituted stereogenic center α to 2-azaarenes. 相似文献
12.
Mika Sakai Masayoshi Mori Dr. Masato Hirai Dr. Naoki Ando Prof. Dr. Shigehiro Yamaguchi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(38):e202200728
Two kinds of planarized phenyldithienylboranes, which contain (CH3)2C- or CH2-bridging moieties, were synthesized. The difference of the bridging moieties affects their packing structures and photophysical properties. In particular, the (CH3)2C-bridged derivative exhibits a large Stokes shift, unusual for such planarized compounds, that results from a large structural relaxation in the excited state. A series of π-extended derivatives was synthesized, among which a p-(diphenylamino)phenyl-substituted derivative shows large solvatochromism in the fluorescence spectra, while maintaining high quantum yields even in polar solvents. The Lewis acidity of the phenyldithienylborane derivatives was also assessed by titration with pyridine. The Lewis acidity of the boron center is affected not only by the difference in the steric bulk of the bridging moieties, but also by the electronic effect of the substituents introduced at remote positions relative to the boron atom. These results demonstrate the characteristic features of planarized phenyldithienylboranes as building blocks for boron-based π-electron materials. 相似文献
13.
Jie Wang Denan Li Honggui Yang Shufan Yao Prof. Qianqian Zhu Prof. Masahiro Sadakane Prof. Yanshuo Li Prof. Wataru Ueda Prof. Zhenxin Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(41):e202200618
Zeolitic octahedral metal oxides are inorganic crystalline microporous materials with adsorption and redox properties. New ϵ-Keggin nickel molybdate–based zeolitic octahedral metal oxides have been synthesized. 31P NMR spectroscopy shows that reduction of MoVI-based molybdates forms an ϵ-Keggin polyoxometalate that immediately transfers to the solid phase. Investigation of the formation process indicates that a low Ni concentration, insoluble reducing agent, and long synthesis time are the critical factors for obtaining the zeolite octahedral metal oxides rather than the ϵ-Keggin polyoxometalate molecule. The synthesized zeolitic nickel molybdate with Na+ is used as the adsorbent, which effectively separates C2 hydrocarbon mixtures. 相似文献
14.
Tairin Kawasaki Naoki Ishida Masahiro Murakami 《Angewandte Chemie (International ed. in English)》2020,59(41):18267-18271
A convenient method is reported to specifically acylate phenolic hydroxyl groups through a radical pathway. When a mixture of an aldehyde and a phenol in ethyl acetate is irradiated with blue light in the presence of iridium and nickel bromide catalysts at ambient temperature, phenoxyl and acyl radicals are transiently generated in situ and cross‐couple to furnish an ester. Aliphatic hydroxy groups remain untouched under the reaction conditions. 相似文献
15.
Naofumi Nishida Yuki Hori Akane Yamauchi Hazuki Fujiwara Makoto Sakurai Yuya Fujiwara Shin-ichi Honda Shunjiro Fujii Hiroyuki A. Sakaue Daiji Kato Tomohiro Yamaguchi Koji Ishibashi Toshifumi Terui Kuei-Yi Lee 《X射线光谱测定》2020,49(1):99-103
Interaction of highly charged ions (HCIs) with surfaces produce various specific phenomena as a consequence of the potential energy that HCI possesses. In the present study, we have observed photon emission, structural, magnetic, and electronic modification on various carbon-based materials such as carbon nanotube by the impact of HCIs using an electron beam ion source named Kobe EBIS installed at the Kobe University. In order to study the potential effect, HCIs of Arq+ (q = 6–16) with the intensity of 0.1–1 nA are projected on the surface with a constant kinetic energy (16 keV). For photon emission measurements, we observed spatial and spectral distribution of visible light emission from the surface during irradiation with HCIs. On the other hand, the structural modification of multi-walled carbon nanotubes (MWCNTs) irradiated with HCIs has been analyzed using a transmission electron microscopy and Raman spectroscopy. Irradiation effects on the resistivity of single MWCNT supported on micrometer scale bridge pattern were also measured. We have also measured magnetic structure of highly oriented pyrolytic graphite irradiated with HCIs using electron spin resonance at low temperature. At the present paper, we will review our recent experimental results on the interaction of HCI with various carbon-based materials. 相似文献
16.
17.
Kenta Yamaguchi Dr. Toshinori Matsushima Dr. Atula S. D. Sandanayaka Yoko Homma Naoki Uchida Prof. Chihaya Adachi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(25):5598-5602
In organic light-emitting diodes (OLEDs) based on materials that show thermally activated delayed fluorescence (TADF), the internal quantum efficiency of 100 % can be obtained without using phosphorescence-based organometallics that contain rare metals. Therefore, with TADF-based emitters, it is possible to fabricate high-performing OLEDs at a lower cost. However, compared with fluorescence- and phosphorescence-based OLEDs, an understanding of degradation mechanisms in TADF-based OLEDs is still insufficient for future commercialization. In particular, it is widely recognized that the development of electron transport materials is crucial for improving OLED characteristics, especially driving voltages and operational durability. In this study, it was demonstrated that the operational durability of TADF-based OLEDs was greatly improved by introducing a triazine-based material of 2,4,6-tris(1,1′-biphenyl-4-yl)-[1,3,5]triazine (pT2T) as a hole-blocking layer (HBL) compared with a conventional HBL material of 2,4,6-tris(biphenyl-3-yl)-[1,3,5]triazine (T2T). Several experiments were carried out to make the reasons of the improved durability clearer, and attributed the improved durability to the shift of a carrier recombination zone from the emitting layer/HBL interface and the suppressed formation of excited-state quenchers in the pT2T HBL, because of the higher electron mobility of pT2T and the better stability of its radical anion state. 相似文献
18.
Dr. Yoji Horii Prof. Dr. Keiichi Katoh Prof. Dr. Yuji Miyazaki Dr. Marko Damjanović Tetsu Sato Prof. Dr. Liviu Ungur Prof. Dr. Liviu F. Chibotaru Prof. Dr. Brian K. Breedlove Prof. Dr. Motohiro Nakano Prof. Dr. Wolfgang Wernsdorfer Prof. Dr. Masahiro Yamashita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(36):8076-8082
Gd3+ complexes have been shown to undergo unusual slow magnetic relaxation processes similar to those of single-molecule magnets (SMMs), even though Gd3+ does not exhibit strong magnetic anisotropy. To reveal the origin of the slow magnetic relaxation of Gd3+ complexes, we have investigated the magnetic properties and heat capacities of two Gd3+-phthalocyaninato triple-decker complexes, one of which has intramolecular Gd3+–Gd3+ interactions and the other does not. It was found that the Gd3+–Gd3+ interactions accelerate the magnetic relaxation processes. In addition, magnetically diluted samples, prepared by doping a small amount of the Gd3+ complexes into a large amount of diamagnetic Y3+ complexes, underwent dual magnetic relaxation processes. A detailed dynamic magnetic analysis revealed that the coexistence of spin–lattice relaxation and phonon-bottleneck processes is the origin of the dual magnetic relaxation processes. 相似文献
19.
Prof. Dr. Junfeng Yang Yuto Mori Prof. Masahiro Yamanaka Prof. Naohiko Yoshikai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(37):8302-8307
A simple cobalt-diphosphine catalyst has been found to efficiently promote intramolecular cyclization of ortho-cyclopropylvinyl- and cyclopropylidenemethyl-substituted benzaldehydes into benzocyclooctadienone and benzocycloheptadienone derivatives, respectively. This ring-opening hydroacylation likely involves aldehyde C−H oxidative addition, olefin insertion, cyclopropane cleavage by β-carbon elimination, and C−C bond-forming reductive elimination, as was supported by mechanistic experiments and DFT calculations. 相似文献
20.
Taishi Nakanishi Dr. Jun Kikuchi Dr. Atsushi Kaga Prof. Dr. Shunsuke Chiba Prof. Dr. Masahiro Terada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(37):8230-8234
A catalytic enantioselective synthesis of β-amino secondary amides was achieved using vinyl azides as the enamine-type nucleophile and chiral N-Tf phosphoramide as the chiral Brønsted acid catalyst through a five-step sequential transformation in one pot. The established sequential transformation involves an enantioselective [4+2] cycloaddition reaction of vinyl azides with N-acyl imines as the key stereo-determining step that is efficiently accelerated by a chiral N-Tf phosphoramide catalyst in a highly enantioselective manner in most cases. Further generation of the iminodiazonium ion intermediate through ring opening of the cycloaddition product and subsequent skeletal rearrangement involving Schmidt-type 1,2-aryl group migration followed by recyclization of the resulting nitrilium ion were also initiated by the same acid catalyst. Final acid hydrolysis of the recyclized products in the same pot gave rise to enantioenriched β-amino amides through C−C bond formation at the α-position of the secondary amides. 相似文献