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61.
Hiroshi Tanaka Tsuyoshi Hasegawa Narumi Kita Hiroko Nakahara Takahiro Shibata Sho Oe Makoto Ojika Koji Uchida Takashi Takahashi 《化学:亚洲杂志》2006,1(5):669-677
An efficient solution‐phase synthesis of rac‐15‐deoxy‐Δ12,14‐PGJ2 (15dPGJ2) derivatives that contain variable α and ω chains based on a polymer‐assisted strategy and their neurite‐outgrowth‐promoting activity are described. The strategy for the synthesis of PGJ2 derivatives involves the use of a vinyl iodide bearing cyclopentenone as a key intermediate, which undergoes Suzuki–Miyaura coupling and subsequent Lewis acid catalyzed aldol condensation for incorporation of the ω and α chains, respectively. For easy access to the PGJ2 derivatives, a polymer‐supported catalyst and scavengers were adapted for use in these four diverse steps, in which workup and purification can be performed by simple filtration of the solid‐supported reagents. By using this methodology, we succeeded in the synthesis of 16 PGJ2 derivatives with four alkyl boranes and four aldehydes. The neurite‐outgrowth‐promoting activity of the 16 synthetic compounds in PC12 cells revealed that the side‐chains play a major role in modulating their biological activity. The carboxylic acid on the α chain improved the biological activity, although it was not absolutely required. Furthermore, a PGJ2 derivative with a phenyl moiety on the ω chain was found to exhibit an activity comparable to that of natural 15dPGJ2. 相似文献
62.
Ruthenium‐Catalyzed Cycloisomerization of 2,2′‐Diethynyl‐ biphenyls Involving Cleavage of a Carbon–Carbon Triple Bond
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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
63.
Toward Fluorescence‐Based High‐Throughput Screening for Enantiomeric Excess in Amines and Amino Acid Derivatives
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Elena G. Shcherbakova Dr. Valentina Brega Dr. Tsuyoshi Minami Sara Sheykhi Prof. Dr. Tony D. James Prof. Dr. Pavel Anzenbacher Jr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10074-10080
A highly accurate and reliable screening method for enantiomeric excess of amine derivatives in the presence of water is reported. The fluorescence‐based screening system has been realized by self‐assembly of chiral diol‐type dyes (BINOL, VANOL and VAPOL), 2‐formylphenylboronic acid, and chiral amines forming iminoboronate esters. The structure and chirality of the amine analytes determine the stability of the diastereomeric iminoboronate esters, which in turn display differential fluorescence. The fluorescence signal reflects the enantiomeric purity of the chiral amines and was utilized in high‐throughput arrays. The arrays were able to recognize enantiomeric excess of amines, amino esters, and amino alcohols. In addition to qualitative analysis, quantitative experiments were successfully performed. Studies of the role of additives such as water or citrate were carried out to gain insight into the stability of the iminoboronate esters. It is shown that the above additives destabilize less stable esters while the stable esters remain unchanged. Thus, the presence of water and citrate leads to increased difference between the diastereomeric iminoboronates and contributes to the enantiodiscrimination of the chiral amines. 相似文献
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Prof. Dr. Tomoaki Tanase Dr. Kanako Nakamae Yume Okawa Mami Hamada Dr. Arimasa Matsumoto Prof. Dr. Takayuki Nakajima Prof. Dr. Takuya Nakashima Prof. Dr. Tsuyoshi Kawai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202104060
A P-stereogenic linear tetraphosphine tetraoxide, (R,R)- or (S,S)-dpmppm(=O)4, was synthesized to prepare C2 dinuclear M(hfa)3 complexes (M=Eu, Tb, Y) as the first example of lanthanide(III) complexes with P-chiral multidentate phosphine oxides. The mononuclear M(hfa)3 complexes (M=Eu, Y) with a P-chiral diphosphine dioxide, tpdpb(=O)2, were also prepared, and comparison of their photophysical properties for the EuIII complexes revealed that significant chiral induction from the P-chiral centers arises on the achiral M(hfa)3 units through intramolecular π-π stacking constraint in the dinuclear system. 相似文献
67.
In this paper, we present examples of codes all of whose weight classes support 1‐designs, with duals whose classes include two that support 2‐designs. We can find these examples in the triply even binary codes of length 48, which have been classified by Betsumiya and Munemasa. 相似文献
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Abstract Novel poly(vinylsulfide)s were prepared by addition polymerization using 2,5-bis(2-thia-3-butenyl)-1,4-dithiane (TBD) with a radical initiator for an optical polymer having a high refractive index (nD) and Abbe number (v). Homopolymerization of TBD (72.9% conversion) and copolymerization with acrylonitrile or acrylates having nonpolar groups (50.4–81.3% conversion according to the comonomers used) in a limited composition range yielded hard and transparent polymers suitable for application in optics. The methacrylates used yielded no polymeric product as a result of the copolymerization. The obtained polymers had Tg, nD and v ranging between 41.0–124.0°C, 1.678–1.546 and 34.1–43.8, respectively, except that poly(TBD) did not exhibit Tg below 200°C, and it had the highest nD Most of the polymers have higher nD and v than those of other conventional optical polymers and moreover, their values are comparable to those of flint glasses. The copolymerizability of TBD and the group contribution to nD and v are discussed based on the Q-e scheme and on the Lorentz-Lorenz equation, respectively. This work shows that TBD serves as a useful material for the preparation of polymers having high nD and v along with a Tg of more than 100°C, and that the polymers thus obtained are promising optical materials. 相似文献
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