Division of Organic Chemistry, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pashan, Pune-411008 (India), Fax: (+91) 20-25902629.
Chemistry. 2013 Sep 16;19(38):12867-74. doi: 10.1002/chem.201301058. Epub 2013 Aug 9.
Investigation of the intermolecular acyl-transfer reactivity in molecular crystals of myo-inositol orthoester derivatives and its correlation with crystal structures enabled us to identify the essential parameters to support efficient acyl-transfer reactions in crystals: 1) the favorable geometry of the nucleophile (-OH) and the electrophile (C-O) and 2) the molecular assembly, reinforced by C-H⋅⋅⋅π interactions, which supports a domino-type reaction in crystals. These parameters were used to identify another reactive crystal through a data-mining study of the Cambridge Structural Database. A 2:1 co-crystal of 2,3-naphthalene diol and its di-p-methylbenzoate was selected as a potentially reactive crystal and its reactivity was tested by heating the co-crystals in the presence of solid sodium carbonate. A facile intermolecular p-toluoyl group transfer was observed as predicted. The successful identification of reactive crystals opens up a new method for the detection of molecular crystals capable of exhibiting acyl-transfer reactivity.
我们研究了肌醇邻苯二甲酸酯衍生物的分子晶体中的分子间酰基转移反应性，并将其与晶体结构相关联，从而确定了支持晶体中高效酰基转移反应的基本参数：1）亲核试剂（-OH）和亲电试剂（C-O）的有利几何形状，以及 2）由 C-H···π 相互作用增强的分子组装，该组装支持晶体中的多米诺型反应。这些参数用于通过对剑桥结构数据库进行数据挖掘研究来识别另一个反应性晶体。通过选择 2,3-萘二酚及其二对甲基苯甲酸酯的 2:1 共晶作为潜在的反应性晶体，并在存在固体碳酸钠的情况下加热共晶来测试其反应性。正如预期的那样，观察到了易于进行的分子间对甲苯酰基转移。反应性晶体的成功鉴定为检测能够表现出酰基转移反应性的分子晶体开辟了一种新方法。
