- 著者
- 林 貴昭 尾島 克二 紺野 勝弘 間中 明彦 山口 健太郎 山田 幸子 高山 浩明
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.40, no.11, pp.2932-2936, 1992-11-25 (Released:2008-03-31)
- 参考文献数
- 16
- 被引用文献数
- 5 4
A new synthesis of 24-fluoro-1α, 25-dihydroxyvitamin D2 (4a) and its 24-epimer (4b) is described. Starting with 1α, 3β-bis[(tert-butyldimethylsilyl)oxy]-24-norchol-5, 7-dien-23-al (5), a mixture of 4a and 4b was obtained in 3% overall yield in 6 steps. Reversed-phase HPLC cleanly separated the mixture into the two C-24 epimers. The X-ray crystallographic analysis of the 4-phenyl-1, 2, 4-triazoline-3, 5-dione (PTAD) adduct 11b, which was derived from the ester 6, unambiguously determined the configuration at C-24 of this compound. Based on the X-ray analysis, the configuration at C-24 of 4a and 4b was unequivocally determined.
- 著者
- 紺野 勝弘 尾島 克二 林 貴昭 高山 浩明
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.40, no.5, pp.1120-1124, 1992-05-25 (Released:2008-03-31)
- 参考文献数
- 17
- 被引用文献数
- 15 24
An alternative synthesis of the title compound 2, a highly potent analog of 1α, 25-dihydroxyvitamin D3 (1), is described. Starting with 1α, 3β-bis[(tert-butyldimethylsilyl)oxy]androst-5-ene (8), 2 was obtained in 3.8% total yield through 10 steps. This method provides compound 2 in much higher yield than that reported previously.
- 著者
- 山田 幸子 大森 正幸 高山 浩明
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.27, no.12, pp.3196-3198, 1979-12-25 (Released:2008-03-31)
- 被引用文献数
- 11 14
24, 24-Difluoro-1α, 25-dihydroxyvitamin D3 (1) has been synthesized from 24, 24-difluoro-5β-cholestane-3α, 25-diol (2) as an antimetabolic analogue of 1α, 25-dihydroxyvitamin D3 to study the role of the 24-hydroxylation in the metabolism of vitamin D3.
1 0 0 0 OA 3-スルホレンを利用するジエン構築とその応用
- 著者
- 山田 幸子 高山 浩明
- 出版者
- 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.46, no.9, pp.893-908, 1988-09-01 (Released:2009-11-13)
- 参考文献数
- 76
- 被引用文献数
- 7 8
Recent advances in the chemistry of 3- sulfolene, 2, 5- dihydrothiophene 1, 1-dioxide, are reviewed from a view point of diene synthesis. Reaction of 3- sulfolene α- carbanion generated under a variety of basic conditions with various electrophiles followed by a stereoselective desulfonylation provides a new method for synthesizing (E) -, (E, Z) -, and (E, E) -conjugated dienes with extremely high stereoselectivity. The method is applied to the syntheses of various natural products having a conjugated diene structure. 3-Sulfolenes are used as masked dienes in the syntheses of cyclic compounds including natural products via inter- and intramolecular Diels-Alder reactions. Some other developments of the chemistry of 3-sulfolenes and its benzo analogs, benzo [c] -1, 3-dihydrothiophene 2, 2-dioxides, are briefly reviewed.