Synthesis of monofacially functionalized cyclodextrins bearing amino pendent groups
Synthesis of monofacially functionalized cyclodextrins bearing amino pendent groups
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DOI：
10.1021/jo9711549
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发表时间：
1997-12-12
影响因子：
3.6
通讯作者：
Thatcher, GRJ
中科院分区：
文献类型：
--
作者：
Vizitiu, D;Walkinshaw, CS;Thatcher, GRJ
其中所有伯羟基均被胺侧基取代的环糊精α CD、β CD和γ CD的衍生物可通过与胺直接反应由全-6-溴-6-脱氧-CD衍生物有效地合成。这些ACD衍生品，其中承担六，七！或八个胺侧基，代表感兴趣的仿生受体和催化剂。合成策略依赖于定量转化和有效纯化，如通过制备11个均质ACD衍生物所证明的。合成的局限性和潜在的适应性通过合成几种以上的ACD衍生物至>95%纯度来说明。一种在主面用伯胺官能团全取代的CD的合成路线，全-6-（氨基甲基）-6-脱氧-CD，产生了简单的全-6-氨基-6-脱氧-CD的替代试剂，其更适合于进一步的合成转化。该合成策略进一步适用于制备原型（6 + 1）-ACD衍生物，其中一个主要位置被硫化物基团取代，其余六个主要表面位置被胺侧基取代。
Derivatives of the cyclodextrins, alpha CD, beta CD, and gamma CD, in which all primary hydroxyls are substituted by amine pendant groups, may be synthesized efficiently from the per-6-bromo-6-deoxy-CD derivatives by direct reaction with amines. These ACD derivatives, which bear six, seven! or eight amine pendent groups, represent interesting biomimetic receptors and catalysts. The synthetic strategy relies on quantitative transformation and efficient purification as is demonstrated by preparation of 11 homogeneous ACD derivatives. The limitations of the synthesis and potential adaptations are illustrated by the synthesis of several more ACD derivatives to >95% purity. A synthetic route to a CD persubstituted with primary amine functionalities at the primary face, per-6-(aminomethyl)-6-deoxy-CD, yields an alternative reagent to the simple per-6-amino-6-deoxy-CD, which is more suitable for further synthetic transformations. The synthetic strategy is further adapted to preparation of a prototypical (6 + 1)-ACD derivative in which one primary position is substituted with a sulfide group and the remaining six primary face positions are substituted with amine pendent groups.