Asymmetric synthesis of organosilicon compounds using a C-2 chiral auxiliary
Asymmetric synthesis of organosilicon compounds using a C-2 chiral auxiliary
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DOI：
10.1246/bcsj.70.1393
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发表时间：
1997-06-01
影响因子：
4
通讯作者：
Masuda, S
中科院分区：
文献类型：
--
作者：
Kobayashi, K;Kato, T;Masuda, S
通过一种新的不对称合成方法合成了光学活性的硅烷，该方法涉及带有C2手性助剂的1，3-二氧杂-2-硅杂环庚烷与格氏试剂的非对映选择性开环反应，然后用氢化铝锂（LiAlH 4）还原。（R）-乙基甲基苯基硅烷和（R）-甲基苯基丙基硅烷分别以93%ee和98%ee衍生。本文还介绍了其它光学硅烷的制备方法。用H-1 NMR和/或毛细管GC方法测定了其中一些化合物的最大旋光度。根据立体化学结果，提出了非对映选择性开环反应的机理。
Optically active silanes were synthesized by a novel asymmetric synthesis which involved the diastereoselective ring-opening reaction of 1,3-dioxa-2-silacycloheptanes bearing a C-2 chiral auxiliary with Grignard reagents, followed by a lithium aluminum hydride (LiAlH4) reduction. (R)-Ethylmethylphenylsilane and (R)-methylphenylpropylsilane were derived in 93%ee and 98%ee, respectively. The preparation of the other optical silanes is also described. The maximum rotations of some of them have been determined by H-1 NMR and/or capillary GC methods. A mechanism for a diastereoselective ring-opening reaction is proposed based on the stereochemical results.