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Study for New Lewic acid. Prepared from Bf_8・OEt_2 and Trialkylsilyl derwatives.

由Bf_8·OEt_2和三烷基甲硅烷基衍生物制备新的Lewic酸的研究。

基本信息

批准号：
08672439
负责人：
HORITA Kiyoshi
金额：
$ 1.41万
依托单位：
HEALTH SCIENCES UNIVERSITY OF HOKKAIDO
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

项目摘要

1.Boron trifluoride diethyl etherate (BF_3・Oet_2) and trimethylsilyl triflate are the most representative Lewis acids in many kinds of Lewis acids. We found that these two Lewis acids easily and quickly reacted in acetonitrile to give a new Lewis acid (BF_2(OTf)). This new chemical species was identified by ^1H,^<11>B,^<19>FNMR experiments. When 1 equivalent of boron trifluoride etherate was combinated with 1 equivalent of trimethylsilyl triflate in 1 : 1 ratio in CD_3CN,a methyl signal of CH_3OTf at 0.5 ppm (broad singlet) disappered and one set of doublet (J=7.5 Hz) at 0.2 ppm was observed as a methyl signal of trimethylsilyl fluoride in ^1HNMR.Furthermore, decatet signal (J=7.5 Hz) was observed in ^<19>FNMR based on a trimethylsilyl fluoride. It was found that trialkylsilyl derivatives such as trimethylsilyl methanesulfonate, trimethylsilylmethyl ether, triethylsilane and trimethylallylsilane generally reacted with boron trifluoride in acetonitrile.2.It was found that C-allylglycosidation reaction of methylidopyranosyl derivative with free hydroxy groups proceeded efficiently and stereoselectively when this newly develoved BF_2OTf was used.

1.三氟化硼乙醚(BF_3·OET_2)和三甲基硅基三氟化硅是多种Lewis酸中最具代表性的两种Lewis酸。我们发现这两种Lewis酸在乙腈中反应迅速，得到了一种新的Lewis酸(BF_2(OTF))。这个新的化学物种是通过^1H，^&lt；11&gt；B，^&lt；19&gt；fnmr实验鉴定的。当1当量的三氟化硼乙醚与1当量的三氟化硅按1：1的比例结合在Cd_3CN中时，0.5ppm(宽单重态)的CH3OTf甲基信号消失，0.2ppm的一对二重态(J=7.5赫兹)作为三甲基硅基氟化物的甲基信号。此外，在基于三甲基硅基氟化物的核磁共振中还观察到十重态信号(J=7.5赫兹)。发现三甲基硅基甲烷磺酸盐、三甲基硅基甲醚、三乙基硅烷和三甲基烯丙基硅烷等三烷基硅基衍生物在乙腈中通常与三氟化硼发生反应。2.用这种新开发的BF2OTf研究了甲基吡喃糖衍生物与游离羟基的C-烯丙基糖苷反应，反应效率高，具有立体选择性。