Synthesis of optically active allyltin compounds and their application to enantioselective synthesis of secondary homoallyl alcohols
Synthesis of optically active allyltin compounds and their application to enantioselective synthesis of secondary homoallyl alcohols
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光学活性烯丙基锡化合物的合成及其在高烯丙仲醇对映选择性合成中的应用
DOI：
10.1021/om00126a014
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发表时间：
1985
期刊：
影响因子：
--
通讯作者：
Y. Kawasaki
中科院分区：
文献类型：
--
作者：
J. Otera*;Yukari Yoshinaga;T. Yamaji;T. Yoshioka;Y. Kawasaki
合成了三种具有光学活性的烯丙基锡化合物：R* 2Sn（allyl）2（R*= 2-苯基丁基、2-甲基丁基和3-苯基丁基）、R* R1 Sn（allyl）2（R*= 2-辛基或2-苯基丁基，R1=苯基）和R* R1 R2 Sn（allyl）（R*=2-苯基丁基，R1=苯基，R2=甲基）。根据核磁共振谱，提出了2-苯基丁基和烯丙基之间的α-堆积相互作用。将由此得到的光学活性烯丙基锡化合物与醛反应。在各种烯丙基锡化合物中，只有二烯丙基双（2-苯基丁基）锡表现出良好的对映选择性。反应通过在醛的表面上加成烯丙基进行。其机理可以解释为烯丙基和苯基之间的α-堆积相互作用。
Three types of optically active allyltin compounds, R* 2Sn (allyl) 2 (R*= 2-phenylbutyl, 2-methylbutyl, and 3-phenylbutyl), R* R1Sn (allyl) 2 (R*= 2-octyl or 2-phenylbutyl, R1= phenyl), and R* R1R2Sn (allyl)(R*=2-phenylbutyl, R1= phenyl, R2= methyl), have been synthesized. On the basis of NMR spectra, a-stacking interaction between the 2-phenylbutyl and the allyl groups is suggested. Optically active allyltin compounds thus obtained were subjected to reaction with aldehydes. Among various allyltin compounds, only diallylbis (2-phenylbutyl) tin exhibits good enantioselectivity. The reaction proceeds through addition of the allyl group on the re face of aldehydes. The mechanism can be accounted for on the basis of a-stacking interaction between allyl and phenyl groups.