Synthesis of [1.1.1.1]Metacyclophane Macrocycle
Synthesis of [1.1.1.1]Metacyclophane Macrocycle
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[1.1.1.1]间环芳大环化合物的合成
DOI：
10.1021/jo00104a027
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发表时间：
1994
影响因子：
3.6
通讯作者：
J. J. Stezowski
中科院分区：
文献类型：
--
作者：
A. Rajca;R. Padmakumar;Donald J. Smithhisler;S. R. Desai;C. Ross;J. J. Stezowski
将有机二锂试剂添加到二醛中允许构建[1.1. 1.在环形成步骤中以约40%的产率制备1-间环芳大环，而不采用标准的高稀释技术。本发明的方法是对导致基于苯酚和间苯二酚的环四聚体的常规缩合的补充。[1.1. 1.1间环芳烷1大环是杯[4]芳烃2和杯[4]间苯二酚芳烃3的母体结构，杯[4]芳烃2和杯[4]间苯二酚芳烃3作为与酶和受体相关的复合物形成剂被广泛研究。1，2它们的合成依赖于芳族亲电取代基的成环步骤，随后是官能团转化。3-11现在我们报告一个合成的[1.1。1.1间环蕃大环化合物，基于有机二锂试剂与二醛的加成。特别地，我们描述了四溴取代的[1.1]的合成和固态结构。1.1 jmetacyclophane 8（方案1和图1），使用依赖于亲电芳香族取代的传统合成路线不容易获得。导致8的合成方法应该使新的笼和二维网络的合理构建可行，与新的材料方法有关。12
Additions of organodilithium reagents to dialdehydes allow for construction of [1.1. 1. ljmetacyclo-phane macrocycle in~ 40% yield in the ring forming step, without resort to standard highdilution techniques. The present methodology is complementary to the conventional condensations leading to phenol-and resorcinol-based cyclotetramers.[1.1. 1.1 jMetacyclophane 1 macrocycle is a parent structure to calix [4] arenes 2 and calix [4] resorcinarenes 3, which are widely studied as complex forming agents with relevance to enzymes and receptors. 1, 2 Their synthesis relies on the aromatic electrophilic substitution-based ring forming steps, followed by functional group transformations. 3-11Now we report a synthesis of a [1.1. 1.1 jmetacyclophane macrocycle, based on addition of organodilithium re-agents to dialdehydes. In particular, we describe the synthesis and solid state structure of tetrabromo-substituted [1.1. 1.1 jmetacyclophane 8 (Scheme 1 and Figure 1), which isnot readily available using conven-tional synthetic routes relying on electrophilic aromatic substitution. The synthetic methods leading to 8 should make feasible rational construction of novel cages and two-dimensional networks, relevant to novel approaches to materials. 12