Yuan De-Qi, Immel Stefan, Koga Katzutaka, Yamaguchi Masatoshi, Fujita Kahee
Faculty of Pharmaceutical Sciences, Nagasaki University Bunkyo-machi, Nagasaki 852-8521, Japan.
Chemistry. 2003 Aug 4;9(15):3501-6. doi: 10.1002/chem.200204310.
Beta-cyclodextrin is transannularly disulfonylated at the 6(A)- and 6(B)-positions, and then converted to the corresponding 6(A),6(B)-diiodide and 6(A),6(B)-dithiol. Cross-coupling of the latter two species yields a single head-to-head-coupled beta-cyclodextrin dimer 5 with two sulfur linkers at adjacent 6-methylene carbons. NMR and X-ray analysis revealed the trans-type ("aversive") linkage of both beta-cyclodextrin units. In the solid-state structure of 5.5 MeOH.23 H(2)O, the undistorted cyclodextrin macrocycles feature almost parallel ring planes pointing away from each other, leaving 5 with a "handcuff-like" appearance of approximate C(2) symmetry. This work represents the first successful crystallographic study on a cyclodextrin dimer.
β-环糊精在6(A)和6(B)位进行跨环二磺酰化，然后转化为相应的6(A),6(B)-二碘化物和6(A),6(B)-二硫醇。后两种物质的交叉偶联产生了一个单头对头偶联的β-环糊精二聚体5，在相邻的6-亚甲基碳上有两个硫连接基。核磁共振和X射线分析揭示了两个β-环糊精单元的反式（“厌恶型”）连接。在5·5MeOH·23H₂O的固态结构中，未变形的环糊精大环具有几乎相互背离的平行环平面，使5呈现出近似C₂对称性的“手铐状”外观。这项工作代表了对环糊精二聚体的首次成功晶体学研究。
