Chiral discrimination of cryptochiral saturated quaternary and tertiary hydrocarbons by asymmetric autocatalysis
Chiral discrimination of cryptochiral saturated quaternary and tertiary hydrocarbons by asymmetric autocatalysis
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DOI：
10.1021/ja061429e
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发表时间：
2006-05-10
影响因子：
15
通讯作者：
Soai, Kenso
中科院分区：
文献类型：
--
作者：
Kawasaki, Tsuneomi;Tanaka, Hiroyuki;Soai, Kenso
饱和烃的手性鉴别一直很难建立，或者根本不可能建立。隐手性5-乙基-5-丙基十一烷1，即（正丁基）乙基（正己基）（正丙基）甲烷，是一种手性饱和季烃，已知在280 ~ 580 nm之间几乎没有可检测的旋光度值，通过嘧啶烷醇的不对称自催化实现了其首次手性鉴别。确定了1的绝对构型。在（R）-或（S）-1存在下，嘧啶-5-甲醛与二异丙基锌反应分别得到（S）-和（R）-嘧啶基烷醇，ee值分别为91−97%。因此，不对称自催化作用是一种强有力的工具，手性饱和烃的歧视。
Chiral discrimination of saturated hydrocarbons has been very difficult to establish, or has not been possible at all. The first chiral discrimination of cryptochiral 5-ethyl-5-propylundecane1, that is, (n-butyl)ethyl(n-hexyl)(n-propyl)methane, a chiral saturated quaternary hydrocarbon, which is known to exhibit practically no detectable value of optical rotation between 280 and 580 nm, has been accomplished by asymmetric autocatalysis of pyrimidyl alkanol. The absolute configuration of1has been determined. In the presence of (R)- or (S)-1, the reaction between pyrimidine-5-carbaldehyde and diisopropylzinc affords (S)- and (R)-pyrimidyl alkanol with 91−97% ee, respectively. Thus, asymmetric autocatalysis serves as a powerful tool for the chiral discrimination of saturated hydrocarbons.