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Utilization of Meso Substrates by Catalytic Asymmetrization Reaction

通过催化不对称反应利用内消旋底物

基本信息

批准号：
07672255
负责人：
KOU Hiroya
金额：
$ 1.47万
依托单位：
TOHOKU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07672255/
关键词：
meso diol asymmetric isomerization reaction chiral BINAP cationic rhodium complex 4-hydroxy-2-cyclochexenone tropane alkalid physoperuvine meso endo diol bis-silyl ether physopervine ロジウム触媒 1,3-水素移動フィゾペルビンシクロペンテノンメソ型ジオールシクロ

项目摘要

The asymmetric olefin migration reaction catalyzed by the cationic Rh-complex ligated with chiral BINAP had been investigated. At the beginning, the diol and the analogus which were easily prepared from the cyclopentadiene and benzoquione were used as the substrates.The following facts were discovered during investigation :1) The optical yield was 43%, when the diol was used as the substrate.2) The almost perfect results were obtained, when the bis-siltl ethers were used.3) The optical yield does not related to the bulkiness of the silyl functional group.4) The bis-alkyl ethers did not bring about good enantiomeric excess.5) The bis-ester did not work at all.6) The course of the olefin migration was inversely between the diol and the bis-silyl ether.Next, this methodology was further applied to the 7-membered meso-ene-diol. The first enantiomeric synthesis of the tropane alkaloid, physoveruvine was achieved from the isomerized product.

研究了阳离子rh配合物与手性BINAP连接催化的不对称烯烃迁移反应。首先以环戊二烯和苯并醌易于制备的二醇及其类似物为底物。研究发现：1)以二醇为底物时，光收率为43%。2)当使用双静止醚时，获得了几乎完美的结果。3)光产率与硅基官能团的体积无关。4)双烷基醚对映体的过量反应不明显。这双酯根本不起作用。6)烯烃在二醇和双硅醚之间的迁移过程是相反的。接下来，将该方法进一步应用于7元间苯二醇。从异构化产物中首次合成了tropane生物碱，physoveruvine。