Luo Na, Ao Yu-Fei, Wang De-Xian, Wang Qi-Qiang
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Chemistry. 2022 Jan 13;28(3):e202103303. doi: 10.1002/chem.202103303. Epub 2021 Nov 8.
Since its discovery two decades ago, anion-π interaction has been increasingly recognized as an important driving force. Extensive theoretical and experimental efforts on the ground-state anion-π binding and recognition have laid the bases for exploring its relevance in catalysis. Accordingly, the concept of "anion-π catalysis" that employing an electron-deficient π surface (π-acidic surface) for anionic reaction intermediate and transition state stabilization has emerged. This article shortly reviews the emergence and development of this concept, aiming to provide an emphasis on the general concept and key progress in this exciting area. To highlight the essential contribution of anion-π interactions, the contents are organized according to their role engaged in catalytic process, for example from both ground-state and transition-state stabilization to solely transition-state stabilization, mainly by a single π-face, and to cooperative π-face activation. A concluding remark and outlook on future development of this field is also given.
自二十年前被发现以来,阴离子-π相互作用日益被视为一种重要的驱动力。在基态阴离子-π结合与识别方面进行的广泛理论和实验工作,为探索其在催化中的相关性奠定了基础。相应地,“阴离子-π催化”的概念应运而生,即利用缺电子的π表面(π酸性表面)来稳定阴离子反应中间体和过渡态。本文简要回顾了这一概念的出现与发展,旨在强调这一令人兴奋的领域中的一般概念和关键进展。为突出阴离子-π相互作用的重要贡献,内容根据其在催化过程中的作用进行组织,例如从基态和过渡态的稳定到仅过渡态的稳定,主要通过单个π面,再到协同π面活化。本文还给出了关于该领域未来发展的总结性评论与展望。