权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

ゲルセミウムアルカロイド類のバイオミメティックな合成研究

钩吻生物碱的仿生合成研究

基本信息

批准号：
06772061
负责人：
北島満里子
金额：
$ 0.58万
依托单位：
Chiba University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Encouragement of Young Scientists (A)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至无数据
项目状态：
已结题

项目摘要

漢薬'胡満〓'として知られるゲルセミウム属植物に含有される、複雑で歪みのかかった特異な構造を持つゲルセミウムアルカロイド類のバイオミメティックな合成研究の一環として、今回微量新塩基である11-Methoxygelsemamide(Humantenine型塩基)、最も歪のかかったGelsemine、並びにGelsemicine(Gelsedine型塩基)の化学合成研究を行った。1.11-Methoxygelsemamideの合成研究:Gardnerine(Sarpagine-type alkaloid)より、C/D環開裂、オキシインドールへの酸化的転位、エチリデン側鎖の異性化、Na-メトキシオキシインドールへの変換により11-Methoxygelsemamideの前駆体と考えられるHumantenirine(Gelsemium alkaloid)へと12工程収率10%で大量に導いた。つづいてこれをNeOH中NaOMeで処理することにより、Na-C2 seco indole systemを有する11-Methoxygelsemamideを収率78%にて合成することができた。以上の様に11-Methoxygelsemamideのバイオミメティックな化学合成に成功し、その結果についてはTetrahedronに掲載済みである。2.Gelsemine骨格構築の研究:Gardnerineの6位への酸素官能基、硫黄官能基の導入には成功しているが、今のところ鍵反応であるGelsemineの最も特徴的なC6-C20結合の形成には至っていない。3.Gelsemicineの合成研究:GardnerineのC/D環開裂、オキシインドールへの酸化的転位、エチリデン二重結合の異性化、D環の開環、再閉環によりGelsedine型塩基の生合成中間体と考えられるGelselegine型化合物へと導いた。さらに21位炭素の酸化的脱離、イミンの還元、Na-メトキシ化により15工程でGelsemicineへの生合成仮説に沿った変換に成功した。この結果はJ.C.S.Perkin Trans.1に掲載済みである。

In this paper, we know that some plants of the genus Lepidoptera have been found to contain antigens, and that they have been used in the production of synthetic materials. This time, the trace amount of the new gene 11-Methoxygelsemamide (humane base), the most accurate one, the most accurate one, the most accurate one. The chemical synthesis of Gelsemicine (Gelsedine type radical) was studied in this paper. Study on the synthesis of 1.11-Methoxygelsemamide: Gardnerine (Sarpagine-type alkaloid), Na- D, (Gelsemium alkaloid), (Gelsemium alkaloid), 12, 10%, 10%, 10%, 10%, 10%, 10%, 10%, 10%, 10%. The percentage of patients with 11-Methoxygelsemamide errors in NeOH is 78%, while that in Na-C2 seco indole system is 78%. The results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results showed that the chemical synthesis was successful, and the results 2.Gelsemine bone structure analysis study: Gardnerine 6 amino acid functional groups, sulfur functional groups were successfully introduced into the bone marrow, and now the most specific C6-C20 combination of the most specific Gelsemine was formed. Study on the synthesis of 3.Gelsemicine: the cleavage of Gardnerine, the site of acidification, the double combination of synthesis, the synthesis of Gelselegine, the synthesis of Gelselegine, and the synthesis of Gelselegine. in the study of synthesis of Gelselegine, the synthesis of Gelselegine was studied. The separation of 21-position carbon acidizing, the acidification of Na-, the synthesis of 15 engineering materials, the synthesis of carbon compounds, and the success of carbon acidification were studied in detail. The results show that J.C.S.Perkin Trans.1 has a negative impact on the performance.