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Studies on synthesis of heterocycles and carbocycles by sequential reactions using unsaturated esters

不饱和酯连续反应合成杂环和碳环的研究

基本信息

批准号：
23550054
负责人：
YAMAZAKI SHOKO
金额：
$ 3.33万
依托单位：
Nara University of Education
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2011
资助国家：
日本
起止时间：
2011 至 2013
项目状态：
已结题

项目摘要

New efficient cyclization reactions using highly reactive alfa,beta-unsaturated esters by sequential bond formations has been developed.The reaction of unsaturated esters such as ethenetricarboxylates, 2-phosphonoacrylate and 2-(trifluoromethyl)acrylate with diethyl azodicarboxylate and PPh3 gave pyrazolines efficiently. Reaction of allyl ethenetricarboxylates and the amides with Lewis acids such as TiCl4, TiBr4 and AlCl3 gave 3,4-trans-halogenomethyl 2-oxotetrahydrofuran and pyrrolidine derivatives stereoselectively in high yields. The stereochemistries were determined by NOE experiments. Reaction of (E)/(Z)-2-butenyl esters with AlCl3 or FeCl3 gave 3,4-trans 4-(1-chloroethyl) tetrahydro-2-oxofuran diastereoisomers stereospecifically. Reaction of (E)/(Z)-2-butenyl and 2-pentenyl amides with ZnI2 gave 3,4-trans 4-(1-iodoethyl and propyl) tetrahydro-2-oxopyrrolidine diastereoisomers stereospecifically.These reactions represent efficient ways to construct potentially useful compounds.

开发了利用高反应性α,β-不饱和酯通过连续成键的新型高效环化反应。乙烯三羧酸酯、2-膦酰基丙烯酸酯和2-(三氟甲基)丙烯酸酯等不饱和酯与偶氮二甲酸二乙酯和PPh3的反应有效地生成吡唑啉。乙烯三羧酸烯丙酯和酰胺与路易斯酸（例如 TiCl4、TiBr4 和 AlCl3）反应，以高产率立体选择性地生成 3,4-反式卤代甲基 2-氧代四氢呋喃和吡咯烷衍生物。立体化学通过NOE 实验确定。 (E)/(Z)-2-丁烯酯与AlCl3或FeCl3反应立体有择地得到3,4-反式4-(1-氯乙基)四氢-2-氧代呋喃非对映异构体。 (E)/(Z)-2-丁烯基和2-戊烯基酰胺与ZnI2反应立体定向地产生3,4-反式4-(1-碘乙基和丙基)四氢-2-氧代吡咯烷非对映异构体。这些反应代表了构建潜在有用化合物的有效方法。