Knochel Paul, Karaghiosoff Konstantin, Manolikakes Sophia
Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377, Munich, Germany,
Top Curr Chem. 2013;334:171-90. doi: 10.1007/128_2012_394.
Frustrated Lewis pairs (FLPs), sterically encumbered Lewis acid and base combinations, gained importance due to their ability to activate molecular hydrogen. This property is used in organic synthesis to perform metal-free catalytic hydrogenation of imines, quinolines, or enamines. Moreover, it is possible to perform selective C-H activations using different sterically hindered Lewis acid/base pairs. Thus, the combination of organometallic reagents with different boranes can be used to functionalize selectively a variety of tertiary amines. By combination of sterically hindered metal amides of the type TMP-Met (TMP = 2,2,6,6-tetramethylpiperidyl, Met = Li, MgCl, ZnCl) with the Lewis-acid BF3·OEt2 it is possible to metalate selectively a large number of aromatic N-heterocycles, such as pyridines and quinolines.
受阻路易斯酸碱对(FLPs),即空间位阻较大的路易斯酸和碱的组合,因其能够活化分子氢而变得重要。这种性质在有机合成中用于对亚胺、喹啉或烯胺进行无金属催化氢化。此外,使用不同的空间位阻路易斯酸/碱对进行选择性C-H活化也是可能的。因此,有机金属试剂与不同硼烷的组合可用于选择性地官能化多种叔胺。通过将TMP-Met型(TMP = 2,2,6,6-四甲基哌啶基,Met = Li、MgCl、ZnCl)的空间位阻金属酰胺与路易斯酸BF3·OEt2组合,可以选择性地使大量芳香族N-杂环(如吡啶和喹啉)金属化。