著者

西山 久雄

出版者

公益社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.77, no.2, pp.189-191, 2019-02-01 (Released:2019-02-08)

参考文献数

16

被引用文献数

1

著者

長瀬 博 松本 和久 西山 久雄

出版者

The Society of Synthetic Organic Chemistry, Japan

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.54, no.12, pp.1055-1066, 1996-12-01 (Released:2009-11-16)

参考文献数

44

被引用文献数

6 10

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Just after the discovery of PGI2, we started to find chemically and metabolically stable PGI2 derivatives with longer duration of action. Extensive studies led us to a new class of stable PGI2 analogue, 5, 6, 7-trinor-4, 8-inter-m-phenylenePGI2 that has a phenol moiety instead of enol-ether linkage in PGI2. In order to accomplish synthesis of the m-phenylenePGI2, novel synthetic methods were developed, for instance, ortho-selective metal-halogen exchange reaction of bromoanisoles by means of Grignard reagent, copper-catalyzed SN2' cyclization to prepare dihydrocyclopenta [b] benzofuran, and regioselective and stereo-selective elongation of ω-side chain by Prins reaction. Further efforts were devoted to synthesize derivatives of m-phenylenePGI2 with enhanced pharmacological activity and less adverse reaction. Finally, we attained to Beraprost sodium which is the first launched drug as an orally active PGI2. This paper will focus on the study of total syntheses of m-phenylenePGI2.

著者

本山 幸弘 西山 久雄

出版者

The Society of Synthetic Organic Chemistry, Japan

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.61, no.4, pp.343-351, 2003-04-01 (Released:2009-11-13)

参考文献数

27

被引用文献数

11 13

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Optically active bis (oxazolinyl) phenyl (Phebox) was designed as an anionic N-C-N pincer ligand, and (Phebox) SnMe3 was prepared as its stable precursor. The aqua complexes, (Phebox) RhIIIX2H2O) [X=Cl, Br, F], [(Phebox) MII (H2O)] (BF4) [M=Pd, Pt] and [(Phebox) PtIV (H2O)] (BF4), were synthesized by the oxidative addition or transmetallation of RhI, PdII and PtII precursors with (Phebox) SnMe3 and subsequent ligand exchange reaction. X-ray structure studies revealed that the octahedral structure of RhIII complex is isosteric with the PtIV, and the PdII and PtII complexes are almost the same configuration with a square-planar structure. These aqua complexes acted as efficient catalysts for enantioselective allylation of aldehydes with allyltin reagents, hetero Diels-Alder reaction of Danishefsky's diene with glyoxylates and the aldol-type condensation of tosylmethyl isocyanide with aldehydes. While (Phebox) RhIII (SnMe3) Cl complexes catalyzed the Michael addition of α-cyanopropionates to acrolein.