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Synthetk Studies on Multi Sorts of Biologically Active Cormpounds Using Nitrones Related to Amino Acids and Sugars

氨基酸和糖相关硝酮合成多种生物活性化合物的研究

基本信息

批准号：
15590003
负责人：
TAMURA Osamu
金额：
$ 2.3万
依托单位：
Kanazawa University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

(1)A method for the synthesis cyclic nitrones having multi-oxygen functionalities from herniacetals such as sugars was explored. Thus, the nitrones were prepared by TBAT-mediated desilylative cyclization of ω-mesyloxy-O-tert-butyldiphenylsilyloximes, readily prepared from sugar derivatives by a consecutive treatment with O-tert-butyldiphenylsilylhydroxylamine and with mesyl chloride. As an application of this method, concise synthes of codonopsine, hyacinthacine A_1, and hyacinthacine A_2 were reality accomplished from the cyclic nitrone, which was obtained from protected L-xylose.(2)A cyclic nitrone derived from (S)-phenylglycinol reacted with allyl alcohols in the presence of MgBr_2OEt_2 to give cycloadducts stereoselectively. The reaction was applied to syntheses of monatin (a natural sweetener) and lycoperdic acid. In contrast to cycloaddition with allyl alcohols, reactions of the cyclic nitrone with a-substituted acrylates in the absence of MgBr_2・OEt_2 gave cycloadducts having op … More posite C4-stcreochemistries. The reaction was used for the synthesis of 4-epi-monatin.(3)The first syntheses of (-)-funebrine and (-)-funebral were achieved. The syntheses feature sequential formation of the nitrone from methyl glyoxylate with a gulose-derived oxime, transesterification with (E)-crotyl alcohol, and intramolecular cycloaddition. The major cycloadduct was readily elaborated to amino lactone, the key synthetic intermediate of (-)-funebrine and (-)-funebral.(4)To synthesize (3'R,5'S)-3'-hydroxycotinine, the main metabolite of nicotine, cycloaddition of C-(3-pyridyl)nitrones with (2R)-and (2S)-N-(acryloyl)bornane-10,2-sultam {(2R)-and (2S)-sultam] was examined. Among them, L-gulose-derived nitrone underwent stereoselective cycloaddition with (2S)-sultam to afford the cycloadduct, which was elaborated to (3'R,5'S)-3'-hydroxyeotinine.(5)Applications of Diets-Alder reactions and cycloaddition of nitrones, representative peri-cyclic reactions to synthesis of heterocyclic compounds were reviewed. Less

(1)A探索了由糖等缩醛类化合物合成具有多氧官能团的环状硝酮的方法。因此，硝酮是通过TBAT介导的ω-甲磺酰氧基-O-叔丁基二苯基甲硅烷基肟的脱甲硅烷基环化来制备的，所述ω-甲磺酰氧基-O-叔丁基二苯基甲硅烷基肟容易地由糖衍生物通过用O-叔丁基二苯基甲硅烷基羟胺和甲磺酰氯连续处理来制备。作为该方法的应用，以L-木糖为保护基合成了环硝酮，实现了对可登素、风信子碱A_1和风信子碱A_2的简便合成。(2)A在MgBr_2OEt_2存在下，由（S）-苯基甘氨醇衍生的环状硝酮与烯丙醇反应，立体选择性地得到环加合物。将该反应应用于天然甜味剂莫纳甜和番茄红素的合成。与烯丙醇的环加成反应不同，在MgBr_2·OEt_2存在下，环状硝酮与α-取代丙烯酸酯的环加成反应得到了具有较好的环加成产物 ...更多信息复合C4-结构化学。该反应用于合成4-表莫纳甜。（3）首次合成了（-）-funebrine和（-）-funebral。该合成方法的特点是由乙醛酸甲酯与古洛糖衍生的肟，与（E）-巴豆醇的酯交换反应和分子内环加成反应顺序形成硝酮。主要的环加成物很容易被加工成氨基内酯，氨基内酯是合成（-）-funebrine和（-）-funebral的关键中间体。(4)To合成了烟碱的主要代谢产物（3 'R，5'S）-3'-羟基可替宁，考察了C-（3-吡啶基）硝酮与（2 R）-和（2S）-N-（丙烯酰基）异丁烷-10，2-磺内酰胺（（2 R）-和（2S）-磺内酰胺）的环加成反应。其中，L-古洛糖衍生的硝酮与（2S）-磺内酰胺进行立体选择性环加成反应，得到环加成物，再经环加成反应合成（3 'R，5'S）-3'-羟基肉毒碱。（5）综述了Diets-Alder反应和硝酮环加成反应在杂环化合物合成中的应用。少