General approach to the synthesis of persubstituted hydrophilic and amphiphilic beta-cyclodextrin derivatives.
General approach to the synthesis of persubstituted hydrophilic and amphiphilic beta-cyclodextrin derivatives.
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合成全取代亲水性和两亲性β-环糊精衍生物的一般方法。
DOI：
10.1021/jo010046q
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发表时间：
2001
期刊：
影响因子：
--
通讯作者：
J. Závada
中科院分区：
文献类型：
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作者：
T. Kraus;M. Buděšínský;J. Závada
通过四氧化锇催化的二羟基化，将庚基(2,3,6-三-O-烯丙基)-β-环糊精2转化为庚基[2,3,6-三-O-(2,3-二羟基丙基)]-β-环糊精3。将3的非对映体混合物用高碘酸钠处理，然后用硼氢化钠处理，得到七[2,3,6-三-O-(2-羟乙基)]-β-环糊精5，产率86％。通过TEMPO介导的氧化，化合物5可以定量转化为庚(2,3,6-三-O-羧甲基)-β-环糊精6。同样的反应顺序也适用于庚(2,6-二-O-烯丙基-3-O-甲基)-β-环糊精8、庚(2,3-二-O-烯丙基-6-O-甲基)-β-环糊精12和庚(2,3-二-O-烯丙基-6-O-丁基)-β-环糊精16；以高产率分离出类似的相应羟乙基和羧甲基衍生物。所有产品均被证明化学性质均一。
Heptakis(2,3,6-tri-O-allyl)-beta-cyclodextrin 2 was converted to heptakis[2,3,6-tri-O-(2,3-dihydroxypropyl)]-beta-cyclodextrin 3 by osmium tetroxide-catalyzed dihydroxylation. A diastereomeric mixture of 3 was treated with sodium periodate followed by sodium borohydride to give heptakis[2,3,6-tri-O-(2-hydroxyethyl)]-beta-cyclodextrin 5 in 86% yield. Compound 5 could be quantitatively transformed into heptakis(2,3,6-tri-O-carboxymethyl)-beta-cyclodextrin 6 by TEMPO-mediated oxidation. The same reaction sequence was also applied to heptakis(2,6-di-O-allyl-3-O-methyl)-beta-cyclodextrin 8, heptakis(2,3-di-O-allyl-6-O-methyl)-beta-cyclodextrin 12, and heptakis(2,3-di-O-allyl-6-O-butyl)-beta-cyclodextrin 16; the analogous corresponding hydroxyethyl and carboxymethyl derivatives were isolated in high yields. All products were proved to be chemically uniform.