Yang Hui, Wong Ming Wah
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
Molecules. 2020 Feb 26;25(5):1045. doi: 10.3390/molecules25051045.
The strong, specific, and directional halogen bond (XB) is an ideal in crystal engineering, as well as rational catalyst and drug design. These attributes attracted strong growing interest in halogen bonding in the past decade and led to a wide range of applications in materials, biological, and catalysis applications. Recently, various research groups exploited the XB mode of activation in designing halogen-based Lewis acids in effecting organic transformation, and there is continual growth in this promising area. In addition to the rapid advancements in methodology development, computational investigations are well suited for mechanistic understanding, rational XB catalyst design, and the study of intermediates that are unstable when observed experimentally. In this review, we highlight recent computational studies of XB organocatalytic reactions, which provide valuable insights into the XB mode of activation, competing reaction pathways, effects of solvent and counterions, and design of novel XB catalysts.
强大、特定且具有方向性的卤键（XB）在晶体工程以及合理的催化剂和药物设计中是理想的。在过去十年中，这些特性引发了人们对卤键的浓厚兴趣，并在材料、生物和催化应用中得到了广泛应用。最近，各个研究小组在设计用于实现有机转化的卤素基路易斯酸时利用了XB活化模式，并且在这个有前景的领域中不断发展。除了方法学发展的快速进步外，计算研究非常适合于机理理解、合理的XB催化剂设计以及对实验观察时不稳定的中间体的研究。在这篇综述中，我们重点介绍了XB有机催化反应的近期计算研究，这些研究为XB活化模式、竞争反应途径、溶剂和抗衡离子的影响以及新型XB催化剂的设计提供了有价值的见解。
