Structure-Reactivity Relationship in the Frustrated Lewis Pair (FLP)-Catalyzed Hydrogenation of Imines.
Structure-Reactivity Relationship in the Frustrated Lewis Pair (FLP)-Catalyzed Hydrogenation of Imines.
复制标题
DOI：
10.1002/chem.201600716
复制
发表时间：
2016-05
期刊：
影响因子：
--
通讯作者：
Sebastian Tussing;Karl Kaupmees;J. Paradies
中科院分区：
文献类型：
--
作者：
Sebastian Tussing;Karl Kaupmees;J. Paradies
用动力学方法研究了16-苯环取代的N-亚甲基叔丁胺与B(2，6-F2C6H3)3和分子氢的自诱导受阻Lewis对(FLP)催化加氢反应。用量子力学方法测定了亚胺和相应胺的pKa值，并给出了正比关系。两个速率常数K1(简单催化循环)和K2(自诱导催化循环)与亚胺和胺对之间的pKa差(ΔpKa)或σ参数之间的关联可作为建立亚胺催化加氢反应的结构-活性关系的有用参数。
The autoinduced, frustrated Lewis pair (FLP)-catalyzed hydrogenation of 16-benzene-ring substituted N-benzylidene-tert-butylamines with B(2,6-F2 C6 H3 )3 and molecular hydrogen was investigated by kinetic analysis. The pKa values for imines and for the corresponding amines were determined by quantum-mechanical methods and provided a direct proportional relationship. The correlation of the two rate constants k1 (simple catalytic cycle) and k2 (autoinduced catalytic cycle) with pKa difference between imine and amine pairs (ΔpKa ) or Hammett's σ parameter served as useful parameters to establish a structure-reactivity relationship for the FLP-catalyzed hydrogenation of imines.