著者

Takuya Murai Shohei Hamada Yusuke Kobayashi Takahiro Sasamori Takumi Furuta

出版者

The Pharmaceutical Society of Japan

雑誌

Chemical and Pharmaceutical Bulletin (ISSN:00092363)

巻号頁・発行日

vol.70, no.9, pp.605-615, 2022-09-01 (Released:2022-09-01)

参考文献数

31

被引用文献数

1

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The preparation, optical resolution, and structural investigations of a series of axially chiral biaryl dicarboxylic acids bearing oxygen, sulfur, and selenium atoms were carried out. The crystal structures of sulfur- and selenium-containing derivatives revealed that the carboxy groups of these compounds are located in a co-planar geometry with the fused aromatic rings including the chalcogen atoms. These conformational controls were found to be achieved by chalcogen-bonding interactions between chalcogen atoms in the aromatic rings and oxygen atoms in the carboxy groups. Even in the case of a binaphthofuran derivative, in which the formation of chalcogen-bonding interactions was expected to be negligible, the carboxy groups were also found to be located in a co-planar geometry toward its fused cyclic rings. Natural bond orbital (NBO) analyses of these dicarboxylic acids indicated the formation not only for the chalcogen-bonding interactions for S and Se derivatives, but also the tetrel-bonding interactions between the oxygen atoms in the carboxy groups and the carbon atoms in the fused cyclic rings for all biaryl dicarboxylic acids. These tetrel-bonding interactions were thought to contribute to conformational control in the binaphthofuran derivative. Physical and chiroptical properties such as the racemization barriers and circular dichroism (CD) spectra of these biaryl dicarboxylic acids were also revealed.

著者

Jing-Dong Guo Takahiro Sasamori Yutaro Yamamoto Hiroshi Matsubara Shigeru Nagase Hideki Yorimitsu

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

pp.20150343, (Released:2015-11-16)

被引用文献数

4

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The previously reported palladium-catalyzed silylation of aryl chlorides with silylsilatranes were theoretically reinvestigated by DFT calculations with a focus on the effect of the transannular Si–N coordination on silyl transfer. The Si–N coordination proved to be not so influential as to accelerate the silyl transfer. However, it should be of benefit to use silylsilatranes as silylating agents because of their easy handling and facile preparation.

著者

Michiyasu Sakagami Takahiro Sasamori Heisuke Sakai Yukio Furukawa Norihiro Tokitoh

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.86, no.10, pp.1132-1143, 2013-10-15 (Released:2013-10-15)

参考文献数

62

被引用文献数

27

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1,2-Bis(ferrocenyl)dipnictenes bearing a Pn=Pn π-spacer (Pn: P (1), Sb (2), and Bi (3)) between two ferrocenyl units have been synthesized as stable compounds. Not only their molecular structures and fundamental properties but also their redox behavior have been systematically disclosed. Interestingly, in the reduction region, the dipnictenes showed two pseudo-reversible one-electron redox couples at low temperature, suggesting possible generation of the corresponding radical anion and dianion species. On the other hand, they showed three-step one-electron oxidation processes in the oxidation region. The first two oxidation steps would correspond to those of the two ferrocenyl moieties, while the third step would be that of the Pn=Pn π-spacer moiety, respectively. Thus, these 1,2-bis(ferrocenyl)dipnictenes with a Pn=Pn π-spacer should be stable multiredox systems reflecting unique properties of a double bond between heavier 15 group elements. As a result, all Pn=Pn units (Pn: P, Sb, and Bi) were found to work as a more effective π-spacer than those of 2nd row elements such as C=C and N=N.

著者

Eiko Mieda Takahiro Sasamori Shohei Sase Kei Goto Norihiro Tokitoh

出版者

The Chemical Society of Japan

雑誌

Chemistry Letters (ISSN:03667022)

巻号頁・発行日

vol.40, no.2, pp.196-197, 2011-02-05 (Released:2011-01-22)

参考文献数

18

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We report here the attempted synthesis of a stable 1-fluoro-2-hydrosilene bearing a Bpq group, which is a bulky aryl group bearing a cavity-shaped framework. We have successfully synthesized an overcrowded benzyldifluorosilane as a precursor. Treatment of the benzyldifluorosilane with 2 equiv of t-BuOK in THF afforded the corresponding benzyl anion, the structure of which showed a unique feature as a fluorosilene–KF complex.