Manganese-Catalyzed Hydrogenation of Amides and Polyurethanes: Is Catalyst Inhibition an Additional Barrier to the Efficient Hydrogenation of Amides and Their Derivatives?
Manganese-Catalyzed Hydrogenation of Amides and Polyurethanes: Is Catalyst Inhibition an Additional Barrier to the Efficient Hydrogenation of Amides and Their Derivatives?
复制标题
锰催化的酰胺和聚氨酯的氢化：催化剂抑制是否是酰胺及其衍生物有效氢化的额外障碍？
DOI：
10.1021/acs.organomet.3c00399
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发表时间：
2024-01-22
期刊：
影响因子：
2.8
通讯作者：
Kumar A
中科院分区：
文献类型：
--
作者：
Luk J;Oates CL;Fuentes Garcia JA;Clarke ML;Kumar A
具有N-C =O官能团的酰胺和其他亲电性较差的羰基衍生物的加氢需要在范围和催化活性方面有重大改进，才能成为工业上真正有用的反应。在这里，我们报告了一项研究的结果，该研究检查了含氮化合物（如脂肪胺）作为催化剂抑制剂是否进一步不利于这些反应。在这种情况下，一种对映体纯锰催化剂被用作锰催化剂的原型，这种催化剂以前被证明在酮、n -芳基亚胺和酯的氢化中是有效的。这是通过掺杂模型酯加氢与各种含氮化合物和监测进展来完成的。由此，描述了酰胺和聚氨酯催化氢化的方案，包括导致低水平动力学分辨率的轴向手性酰胺的催化氢化。含氮化合物在催化加氢过程中起抑制剂作用的假设也通过光谱（高压红外（IR），核磁共振（NMR））和质谱研究得到了合理化。
The hydrogenation of amides and other less electrophilic carbonyl derivatives with an N–C=O functionality requires significant improvements in scope and catalytic activity to be a genuinely useful reaction in industry. Here, we report the results of a study that examined whether such reactions are further disadvantaged by nitrogen-containing compounds such as aliphatic amines acting as inhibitors on the catalysts. In this case, an enantiomerically pure manganese catalyst previously established to be efficient in the hydrogenation of ketones, N-aryl-imines, and esters was used as a prototype of a manganese catalyst. This was accomplished by doping a model ester hydrogenation with various nitrogen-containing compounds and monitoring progress. Following from this, a protocol for the catalytic hydrogenation of amides and polyurethanes is described, including the catalytic hydrogenation of an axially chiral amide that resulted in low levels of kinetic resolution. The hypothesis of nitrogen-containing compounds acting as an inhibitor in the catalytic hydrogenation process has also been rationalized by using spectroscopy (high-pressure infrared (IR), nuclear magnetic resonance (NMR)) and mass spectrometry studies.
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