56(P21) 1,4-ジオキシシクロヘキセノイド型キラル合成素子を活用するポリオキシシクロヘキサン天然物の集約的合成(ポスター発表の部)
スポンサーリンク
概要
- 論文の詳細を見る
A series of polyoxygenated cyclohexenoid natural products have been synthesized diastereo-and enantio-selectively in an integrated manner starting from either a synthetic equivalent of chiral cyclohexane-2,5-diene-1,4-diol 2 or a synthetic equivalent of chiral 4-hydroxy-2-cyclohexenone 3 obtained from the meso precursor 1. Thus, starting with (+)-2, all diastereomers of conduritols, including natural conduritols, A 14 and (-)-F 23 as well as unnatural conduritols, D 19, (+)-B 28, (-)-E 25, and (+)-C 32, have been synthesized diastereoselectively in an integrated manner on the basis of the inherent convex-face selectivity exerted by the starting material. Moreover, the same inherent stereochemical nature of (+)-2 has been reflected for the diastereocontrolled construction of some naturally occurring cyclohexenethanol derivatives isolated from some medicinal plants, (-)-cleroindicin E 39, (-)-cleroindicin C 40, and (-)-isocleroindicin E 41, to determine their absolute configuration through the common intermediate (+)-38. (+)-38 has also served as the key intermediate for the diastereocontrolled construction of non-chiral natural products rengyoxide 43, rengyol 44, and cleroindicin A 46 having meso structure. One the other hand, the chiral ketone (-)-3 obtained by the catalytic procedure has been found to serve as an appropriate stating material for the integrated construction of (-)-quinic acid 55 and (-)-shikimic acid 59, occurring in both plants and microorganisms, through the common intermediate 51 on the basis of the same stereochemical background as 2. The enantiomeric α-hydroxyketone (+)-48, generated from the enantiomeric ketone (+)-3, has also been found to serve as an appropriate starting material for the construction of the four cyclohexanemethanol dibenzoate natural products, (-)-zeylenol 66, (+)-pipoxide 67, (-)-tonkinenin A 68 and (-)-varigranol G 69. All of these have been synthesized for the first time from (+)-3 on the basis of its inherent stereochemical nature via the common bromo-ether intermediate 61.
- 天然有機化合物討論会の論文
- 1999-09-01
著者
-
小笠原 國郎
東北大薬
-
上久保 隆
東北大院薬
-
本泉 政敏
東北大院・薬
-
谷口 孝彦
東北大院・薬
-
廣谷 功
東北大院薬
-
本泉 政敏
東北大院薬
-
中島 ひろ美
東北大院薬
-
谷口 孝彦
東北大院薬
-
小笠原 國郎
東北大院薬
-
Ogasawara Kunio
Pharmaceutical Institute Tohoku University
関連論文
- P-32 2-ピリジノン誘導体の官能基化法の開発と含窒素天然物合成への応用(ポスター発表の部)
- 1 シクロヘキサジエノン等価キラル合成素子の創製と天然物合成への活用(口頭発表の部)
- 37 ケトジシクロペンタジエンを活用する生物活性天然物のエナンチオ制御合成(口頭発表の部)
- 13 アルケニルエチレングリコール基質の香月-シャープレス反応と天然物合成への活用(口頭発表の部)
- 43 キラルα-アセチレンアルコール形成法を基軸とするイソプレノイド天然物の合成(口頭発表の部)
- 16 ビシクロ[2.2.1]ヘプタン系キラル素子の合成と天然物合成への活用(口頭発表の部)
- 73 多目的五炭素キラル素子の合成と天然物合成への活用(口頭発表の部)
- P-6 分子内連続反応による小員環構築法の開発と数種のテルペン合成への利用(ポスター発表の部)
- 36 分子内連続反応による多環構造の新構築法の開発と天然物合成への利用(口頭発表の部)
- 25 単一ビシクロ[3.2.1]オクタン型キラル素子による天然物の集約合成 : morphine,yohimbone,vernolepin,ferruginol,calcitriolの新合成(口頭発表の部)