P-63 スピロテヌイペシンAの合成研究(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
Spirotenuipesine A (1) is a trichothecane sesquiterpene which has recently been isolated from Paecilomyces tenuipes (also called Isaria japonica). It possesses an activity in neurotrophic factor biosynthesis, so it can be a lead compound in drug development for neuronal disorders such as Alzheimer's disease. Despite the fascinating activity and structure, total synthesis has not been reported yet. Toward the total synthesis, we planned to construct the carbon skeletal structure of Spirotenuipesine A (1) in short steps, and designed a synthetic approach without using any protecting groups. Starting from the known compound 8, we constructed racemic bicyclic lactone 6 through the reaction of the Ni(0) catalyzed cyclization. To get the spirocompound 4, we designed regioselective and stereoselective 2 steps' coupling reaction with (Z)-dibromide 5. On epoxidation of spirocompound 4, the product was a good crystal, so we analyzed the stereochemistry of three new stereocenters by X-ray crystallographic analysis. By the stereoselective bromohydroxylation and subsequent base treatment, we got epoxide 18 with a correct stereochemistry. Since we could not get next thiocompound 19, we changed the synthetic plan. Epoxidation of bromohydrin 17 gave us a precursor of the key step. In the key DIBAL reduction, lactone 20 was converted to a lactol 21, which was then converted to alcohol 22 by the acid treatment. Fortunately we found that alcohol 22 could be obtained in one step by DIBAL reduction in the presence of diethylalminium chloride. Treatment of 22 with KHMDS gave epoxide 23. Final step with n-BuLi gave racemic Spirotenuipesine A (1). In summary, we could synthesize Spirotenuipesine A (1) in 10 steps from the known compound 8 without using any protecting groups.
- 天然有機化合物討論会の論文
- 2006-09-15
著者
関連論文
- P-18 グルタミン酸拮抗阻害剤Kaitocephalinの大量合成法の開発(ポスター発表の部)
- P-63 スピロテヌイペシンAの合成研究(ポスター発表の部)
- 36 新規GRP78転写抑制物質prunustatin Aに関する研究
- 11 昆虫摂食阻害物質アザジラクチンの合成研究(口頭発表の部)
- ものつくりが目指すバイオサイエンス : 機能解析と有用物質創製を指向して
- 1 天然マクロライド類の全合成研究(口頭発表の部)
- 12 β-ラクタマーゼ型チオエステラーゼによるI型ポリケタイド合成酵素からのatrochrysone carboxylic acidの解離(口頭発表の部)
- P-25 IGF-1依存性がん細胞に対して選択的増殖抑制活性を示すtyroscherinの合成および提出構造の立体化学訂正(ポスター発表の部)
- 36 5員環エーテルを有する天然有機化合物の効率的全合成(口頭発表の部)
- 9C01 抗菌物質Majusculoic acidの合成研究(天然物化学,一般講演要旨)
- 9C04 艀化促進活性を有するSolanoeclepin Aの合成研究(天然物化学,一般講演要旨)
- 9C03 昆虫摂食阻害物質アザジラクチンの合成研究(天然物化学,一般講演要旨)