Induced circular dichroism in chiral N-methyl amides possessing an achiral binaphthyl chromophore and its application to absolute configuration determination of aliphatic chiral amines
Induced circular dichroism in chiral N-methyl amides possessing an achiral binaphthyl chromophore and its application to absolute configuration determination of aliphatic chiral amines
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DOI：
10.1016/j.tetasy.2012.06.013
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发表时间：
2012-07-15
影响因子：
--
通讯作者：
Hosoi, Shinzo
中科院分区：
文献类型：
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作者：
Fujiwara, Toshio;Taniguchi, Yuka;Hosoi, Shinzo
研究了手性伯胺的联萘N-甲基酰胺的诱导圆二色性。CD光谱显示以225 nm为中心的分裂曲线。联萘衍生物的激子手性的符号和原始胺的绝对构型之间有很好的相关性。此外，由分子力学（MM）计算得到的最稳定构象中两个萘基的螺旋方向与由激子手性得到的螺旋方向一致，表明基于MM计算的方法可以用于确定未知的脂肪族手性胺的绝对构型.通过对天然产物D-和L-环丝氨酸的绝对构型的测定，证明了本方法的实用性。(C)2012爱思唯尔有限公司保留所有权利。
Induced circular dichroism (ICD) was observed in binaphthyl N-methyl amides of chiral primary amines. The CD spectra showed split curves centered at 225 nm. A good correlation was found between the sign of the exciton chirality of the binaphthyl derivative and the absolute configuration of the original amine. Furthermore, the screw sense of the two naphthyl groups in the most stable conformer obtained from molecular mechanics (MM) calculation was in agreement with those expected from the exciton chirality, indicating that the method based on MM calculations can be used to determine unknown absolute configurations of aliphatic chiral amines. The practical use of the present method was demonstrated by the determination of the absolute configurations of the natural products, D- and L-cycloserines. (C) 2012 Elsevier Ltd. All rights reserved.