Generation and amplification of optical activity of axially chiral N-(1-naphthyl)-2(1H)-pyrimidinethione by crystallization.
Generation and amplification of optical activity of axially chiral N-(1-naphthyl)-2(1H)-pyrimidinethione by crystallization.
复制标题
通过结晶产生和放大轴向手性 N-(1-萘基)-2(1H)-嘧啶硫酮的光学活性。
DOI：
10.1039/c0ob00262c
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发表时间：
2010
影响因子：
3.2
通讯作者：
T. Fujita
中科院分区：
文献类型：
--
作者：
M. Sakamoto;Fumitoshi Yagishita;Masaru Ando;Y. Sasahara;Norifumi Kamataki;M. Ohta;T. Mino;Yoshio Kasashima;T. Fujita
N-(1-萘基)-2(1H)-嘧啶硫酮的X射线晶体分析表明其空间群为四方且手性P4(3)。由于 C-N 键旋转而导致的外消旋化速率很大程度上受溶剂性质的影响。相对于极性或质子溶剂中的值，非极性溶剂使 ΔG(‡) 值降低约 3.0 kcal mol(-1)。外消旋轴向手性嘧啶硫酮在高温下的结晶导致手性对称性破缺高达91% ee。
X-Ray crystallographic analysis of N-(1-naphthyl)-2(1H)-pyrimidinethione revealed that the space group was tetragonal and chiral P4(3). The rate of racemization due to the C-N bond rotation was considerably influenced by the solvent properties. A nonpolar solvent lowers the ΔG(‡)value by about 3.0 kcal mol(-1) relative to the value in a polar or a protic solvent. The crystallization of racemic axially chiral pyrimidinethione at high temperature led to the chiral breaking of symmetry up to 91% ee.