Absolute helical arrangement of sulfonamide in the crystal

被引:22
作者
Azumaya, I
Kato, T
Okamoto, I
Yamasaki, R
Tanatani, A
Yamaguchi, K
Kagechika, H
Takayanagi, H
机构
[1] Kitasato Univ, Sch Pharmaceut Sci, Tokyo 1088641, Japan
[2] Showa Pharmaceut Univ, Machida, Tokyo 1941543, Japan
[3] Univ Tokyo, Grad Sch Pharmaceut Sci, Bunkyo Ku, Tokyo 1130033, Japan
[4] Chiba Univ, Ctr Chem Anal, Inage Ku, Chiba 2638522, Japan
关键词
D O I
10.1021/ol035509o
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
[GRAPHICS] 1,2-Bis(N-benzenesulfonyl-N-methylamino)benzene (2), which has no fixed asymmetric element, was crystallized from ethyl acetate as chiral crystals belonging to space group P4(1)2(1)2 (No. 92) or P4(3)2(1)2 (No. 96). The array of molecules built by the CH-pi interaction along the c-axis forms an enantiomeric helical superstructure in each individual crystal. The absolute configurations of the chiral crystals of 2 were determined by X-ray crystal structure analysis using the Flack parameter method. The solid-state CD spectra of the chiral crystals in KBr were mirror images. The equilibrium between the two enantiomers in solution is fast during crystallization at ambient temperature, and the energy barrier (DeltaG(not equal)) is estimated to be 11.7 +/- 0.3 kcaVmol (233 K).
引用
收藏
页码:3939 / 3942
页数:4
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