Shen Guang-Bin, Fu Yan-Hua, Zhu Xiao-Qing
College of Chemistry, Nankai University, Tianjin 300071, China.
School of Medical Engineering, Jining Medical University, Jining, Shandong 272000, China.
J Org Chem. 2020 Oct 2;85(19):12535-12543. doi: 10.1021/acs.joc.0c01726. Epub 2020 Sep 11.
In this work, thermodynamic driving forces on 20 possible elementary steps of Hantzsch ester (HEH), benzothiazoline (BTH), and dihydrophenanthridine (PDH) releasing two hydrogen atoms or ions were measured or derived from the related thermodynamic data using Hess' law in acetonitrile. Furthermore, thermodynamic network cards of HEH, BTH, and PDH releasing two hydrogen atoms or ions on 20 elementary steps were first established. Based on the thermodynamic network cards, hydride-donating, hydrogen-atom-donating, and electron-donating abilities of XH and XH, and two hydrogen-atom(ion)-donating abilities of XH are discussed in detail. Obviously, the thermodynamic network cards of HEH, BTH, and PDH not only offer rational data guidance for organic synthetic chemists to properly choose an appropriate reducer among the three reducing agents to hydrogenate various unsaturated compounds but also strongly promote elucidatation of the detailed hydrogenation mechanisms.
在本工作中，在乙腈中测量了1,4-二氢吡啶（HEH）、苯并噻唑啉（BTH）和二氢菲啶（PDH）释放两个氢原子或离子的20个可能基元步骤上的热力学驱动力，或使用赫斯定律从相关热力学数据推导得到。此外，首次建立了HEH、BTH和PDH在20个基元步骤上释放两个氢原子或离子的热力学网络卡。基于这些热力学网络卡，详细讨论了XH和XH₂的供氢化物能力、供氢原子能力和供电子能力，以及XH₂的两种供氢原子（离子）能力。显然，HEH、BTH和PDH的热力学网络卡不仅为有机合成化学家在三种还原剂中正确选择合适的还原剂来氢化各种不饱和化合物提供了合理的数据指导，而且有力地促进了对详细氢化机理的阐释。
