Control of the regioselectivity for new fluorinated amphiphilic cyclodextrins:: Synthesis of di- and tetra(6-deoxy-6-alkylthio)- and 6-(perfluoroalkypropanethio)-α-cyclodextrin derivatives
Control of the regioselectivity for new fluorinated amphiphilic cyclodextrins:: Synthesis of di- and tetra(6-deoxy-6-alkylthio)- and 6-(perfluoroalkypropanethio)-α-cyclodextrin derivatives
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DOI：
10.1021/jo801111b
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发表时间：
2008-09-19
影响因子：
3.6
通讯作者：
Parrot-Lopez, Helene
中科院分区：
文献类型：
--
作者：
Bertino-Ghera, Bernard;Perret, Florent;Parrot-Lopez, Helene
本文报道了十二个新的具有烷基硫基和全氟烷基丙硫基功能的双衍生物和四衍生物α-环糊精分子的合成。为了引入亲脂链，已经开发了一种保护/去保护的飞行策略。偶联反应涉及适当的α-环糊精衍生物与硫代烷基或硫代氟烷基丙烷链之间的反应，这些α-环糊精衍生物被良好的离开基团(二取代基为O-甲苯基或四取代基为碘)在C-6位区域选择性修饰。这些亲核试剂是通过烷基硫代溴化物或全氟烷基环丙烷和异硫代碘化物的原位碱性水解得到的。这些多步骤反应得到了所需的两亲性α-环糊精，总收率为33%至58%。
Twelve new di- and tetraderivatized alpha-cyclodextrin molecules having either alkylthio and perfluoroalkylpropanethio functions at the primary face have been synthesized by using the procedure of Sinay for di-O-debenzylation of perbenzylated alpha-cyclodextrins. A flew strategy of protection/deprotection has been developed for introducing the lipophilic chains. The coupling reaction involves the reaction between the appropriate alpha-cyclodextin derivative, regioselectively modified at C-6 positions by a good leaving group (O-mesityl for disubstituted or iodine for tetrasubstituted derivatives), with the thioalkyl or the thioperfluoroakylpropane chains. These nucleophilic reagents are obtained from the in situ basic hydrolysis of the alkyllsothiouronium bromides or perfluoalkylropropane and the isothiouronium iodides. These multistep reactions give the desired amphiphilic alpha-cyclodextrins in good overall yields of 33% to 58%.