Yang Jin-Dong, Xue Jing, Cheng Jin-Pei
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Chem Soc Rev. 2019 Jun 4;48(11):2913-2926. doi: 10.1039/c9cs00036d.
The past decade has witnessed a booming growth of research activity in catalytic imine reduction, due to the ongoing motivation to find more efficient conversions of the rather unreactive C[double bond, length as m-dash]N bonds to the desired C-N segments found in many pharmaceuticals. While several timely reviews have well documented various C[double bond, length as m-dash]N reduction methodologies with respect to the type of catalyst (acid, base, or transition metal), a detailed discussion of the core role of thermodynamic driving forces in governing these catalyses is still lacking, however. Hence, this tutorial review describes some of the most practical considerations for adjusting reduction thermodynamics by choosing appropriate catalytic strategies, in order to make the target reduction energetically feasible. The combined use of relevant thermodynamic parameters of the substrate imines, hydrogen donors, and catalysts in realizing such a goal is demonstrated on the basis of the energetics of the possible elementary paths. Experimental observations from the literature that are in line with the present energetics-based analyses are exemplified.
在过去十年中，催化亚胺还原领域的研究活动蓬勃发展，这是因为人们一直有动力去寻找更有效的方法，将相对惰性的碳氮双键转化为许多药物中所需的碳氮片段。虽然已有几篇及时的综述很好地记录了各种基于催化剂类型（酸、碱或过渡金属）的碳氮双键还原方法，但对于热力学驱动力在这些催化反应中的核心作用仍缺乏详细讨论。因此，本专题综述描述了一些通过选择合适的催化策略来调整还原热力学的最实际考虑因素，以使目标还原反应在能量上可行。基于可能的基本反应路径的能量学，展示了底物亚胺、氢供体和催化剂的相关热力学参数在实现这一目标中的联合应用。文中还列举了与当前基于能量学分析相符的文献实验观察结果。
