分子旋光度的密度泛函计算及Soman绝对构型确定Calculationof.PDF

2006 年第 64 卷 化 学 学 报 Vol. 64, 2006 第 23 期, 2333～2338 ACTA CHIMICA SINICA No. 23, 2333～2338 ·研究论文· 分子旋光度的密度泛函计算及 Soman 绝对构型确定 *,a b a a 丁晓琴 赵立峰 丁俊杰 陈冀胜 (a 北京药物化学研究所 北京 102205) (b 上海交通大学化学化工学院 上海 200240) 摘要 手性化合物绝对构型的确定一直是有机化学特别是手性药物合成研究过程中经常遇到的问题之一. 利用密度泛 函 DFT/B3LYP 量子化学计算方法, 通过计算两种已知旋光度分子的旋光度, 确认计算条件和验证计算结果的可靠性, 并将此方法应用于 Soman 旋光度的计算. 结合文献报道的 Soman 分子实验旋光度测定结果, 首次采用理论计算方法确 定了梭曼(Soman)分子四个异构体的绝对构型, 分别为 P(R),C(S)-Soman→P( ＋)C( ＋), P(R),C(R)-Soman→P( ＋)C( －), P(S),C(S)-Soman→P( －)C( ＋), P(S),C(R)-Soman→P( －)C( －). 关键词 分子旋光度计算; DFT; 梭曼; 绝对构型 Calculation of Optical Rotation Using Density Functional Theory and Determination of Absolute Configuration for Soman DING, Xiao-Qin*,a ZHAO, Li-Fengb DING, Jun-Jiea CHEN, Ji-Shenga a ( Beijing Institute of Pharmaceutical Chemistry, Beijing 102205) (b School of Chemistry Chemical Technology, Shanghai Jiaotong University, Shanghai 200240) Abstract The determination of absolute configuration for chiral compounds is one of the most important problem in the organic chemisty, especially for chiral drug synthesis. Density functional theory (DFT/B3LYP) method with various basis sets were employed and verified by calculating the optical rotational properties of two tested chiral compounds, and than applied to the calculations of the optical rotational properties of so- man to assign th