Synthesis of two mono-deoxy β-cyclodextrin derivatives as useful tools for confirming DIBAL-H promoted bis-de-O-methylation mechanism

作     者：Su Long Xiao De Min Zhou Ming Yang Fei Yu Li He Zhang Pierre Sinay Yong Min Zhang 

作者机构：State Key Laboratory of Natural and Biomimetic DrugsSchool of Pharmaceutical SciencesPeking University Institut Parisien de Chimie MoleculaireUMR CNRS 7201Universite Pierre et Marie Curie-Paris 64 Place Jussieu Institute for Interdisciplinary ResearchJianghan UniversityWuhan Economic and Technological Development Zone 

出 版 物：《Chinese Chemical Letters》 (中国化学快报（英文版）)

年 卷 期：2012年第23卷第12期

页      面：1315-1318页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070305[理学-高分子化学与物理] 080501[工学-材料物理与化学] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 

基　　金：Financial support of this study from CNRS is gratefully acknowledged 

主　　题：Cyclodextrin (CD) DIBAL-H Deoxy Synthesis Mechanism 

摘      要：Diisobutylaluminium hydride （DIBAL-H） promotes secondary rim regioselective bis-de-O-methylation of permethylated β- cyclodextrin （β-CD） to give diol 2. To gain an insight into the mechanism of this remarkable regioselective behavior, two corresponding permethylated β-CDs with an alcohol function at either 2- or 3-position were synthesized in our previous study. As a step further to this work, the two compounds were subjected to deoxygenation reaction with tributyltin hydride in the present of 2,2＇- azobisisobutyronitrile affording the corresponding 2- and 3-deoxy permethylated β-CD derivatives （19 and 16）. The structures of these two compounds were characterized by 1D and 2D NMR and HRMS. Compounds 16 and 19 were unable to react with DIBAL- H which suggests that O-2A and O-3B are necessary for DIBAL-H promoted bis-de-O-methylation reaction of permethylated β-CD.