Cholesterol recognition and binding by cyclodextrin dimers
Cholesterol recognition and binding by cyclodextrin dimers
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DOI：
10.1021/ja961567b
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发表时间：
1996-09-04
影响因子：
15
通讯作者：
Zhang, BL
中科院分区：
文献类型：
--
作者：
Breslow, R;Zhang, BL
两个单元通过各种间隔基连接的环糊精二聚体显示出与双位底物（例如双-（对硝基苯基）磷酸盐）和带有两个苯基或取代苯基的其他底物的强结合。 1-4 然而，这种环糊精二聚体在结合长疏水性分子（例如甾醇）方面也应该非常有效。例如，胆固醇 (6) 约为。 15 Å 长（包括侧链），而 β-环糊精环的长度约为 15 Å。 7.8 Å 高（方案 1）。因此，两个环之间具有非常短的连接基的环糊精二聚体很可能能够将胆固醇分子协同结合到两个环糊精环中。我们发现情况确实如此。我们通过将6-碘-6-脱氧环七直链淀粉与硫化钠一起加热，构建了二聚体1，产率为44%。 5 该化合物具有预期的 1H-NMR 谱图和正确的 FAB-MS 谱图，M+ 1) 2268。它是 BNS 4 的良好配体（表 1），特别是双（金刚烷基乙基）磷酸-
Cyclodextrin dimers in which the two units are linked by various spacers have shown strong binding of ditopic substrates such as bis-(p-nitrophenyl) phosphate and other substrates carrying two phenyl groups or substituted phenyl groups. 1-4 However, such cyclodextrin dimers should also be very effective at binding long hydrophobic molecules such as sterols. For example, cholesterol (6) is ca. 15 Å long, including the side chain, while a β-cyclodextrin ring is ca. 7.8 Å high (Scheme 1). Thus a cyclodextrin dimer with a very short linker between the two rings might well be able to bind a cholesterol molecule cooperatively into the two cyclodextrin rings. We have found that this is the case.We constructed dimer 1 in 44% yield by heating 6-iodo-6-deoxycycloheptaamylose with sodium sulfide. 5 The compound had the expected 1H-NMR spectrum and the correct FAB-MS spectrum with M+ 1) 2268. It was a good ligand (Table 1) for BNS 4, and particularly for the bis (adamantylethyl) phos-