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SYNTHESIS OF SESQUITERPENS BASED ON A UNIQUE REACTION OF CYCLIC PHOSPHONIUM YLIDES

基于环状磷叶立德的独特反应合成倍半萜

基本信息

批准号：
11650889
负责人：
YAMAMOTO Iwao
金额：
$ 2.24万
依托单位：
SHINSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

The diastereoselective tandem Michael-intramolecular Wittig reactions of a five-membered cyclic phosphonium ylide 2 using 8-phenylmenthyl enoates were examined. The reaction of the phosphonium ylide with 8-phenylmenthyl cinnamate followed by the hydrolysis of the resulting enol ether afforded (3R,4S)-4-(diphenylphosphinyl)-3-phenyl cycloheptanone as the major isomer. The diastereoselectivity of the initial tandem reactions was estimated to be 94 : 6 from the ^<31>P NMR of a mixture of the diastereomeric ketal derivatives which were obtained by the reaction of (3R,4S)-4-(diphenylphosphinyl)-3-phenyl cycloheptanone with (2R,3R)-2,3-butanediol, and the absolute configuration of the major isomer was determined by the single crystal X-ray analysis. Similar reactions using some 8-phenylmenthyl alkenoates were attempted. As a result, it was clarified that the corresponding trans-ketones were obtained and that the diastereomer ratios of their ketal derivatives were 60 : 40-73 : 27. On the other hand, reactions of five and six membered cyclic phosphonium aza-ylides with phenyl thiobenzoate and aryl thiocinnamate gave acylated products. On the other hand, the reactions of cyclic phosphonium aza-ylides with phenyl alkenylthioesters gave com enamino phosphine oxide derivatives. Furthermore, the reactions of five-and six-membered cyclic iminophosphoranes, with β-dicarbonyl compounds gave enamino phosphine oxide derivatives in good yields. The enamino phosphine oxide were stereoselectively converted to 1,6- and 1,7-dienes.

研究了使用 8-苯基薄荷基烯酸酯的五元环鏻叶立德 2 的非对映选择性串联 Michael-分子内 Wittig 反应。鏻叶立德与8-苯基薄荷基肉桂酸酯反应，随后水解所得烯醇醚，得到(3R,4S)-4-(二苯基次膦基)-3-苯基环庚酮作为主要异构体。根据通过(3R，4S)-4-(二苯基次膦基)-3-苯基环庚酮与(2R，3R)-2，3-丁二醇反应获得的非对映异构缩酮衍生物的混合物的31 P NMR，初始串联反应的非对映选择性估计为94∶6，并且绝对值主要异构体的构型通过单晶X射线分析确定。尝试使用一些8-苯基薄荷基烯酸酯进行类似的反应。结果表明，得到了相应的反式酮，其缩酮衍生物的非对映异构体比例为60:40-73:27。另一方面，五元和六元环氮杂叶立德与硫代苯甲酸苯酯和硫代肉桂酸芳基酯反应得到酰化产物。另一方面，环状磷鎓氮杂叶立德与苯基烯基硫酯的反应得到了comenamino 氧化膦衍生物。此外，五元和六元环状亚氨基正膦与β-二羰基化合物的反应以良好的收率得到烯胺氧化膦衍生物。烯胺氧化膦立体选择性地转化为1,6-和1,7-二烯。