Manganese-Catalyzed Hydrogenation of Amides and Polyurethanes: Is Catalyst Inhibition an Additional Barrier to the Efficient Hydrogenation of Amides and Their Derivatives?,Organometallics

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Manganese-Catalyzed Hydrogenation of Amides and Polyurethanes: Is Catalyst Inhibition an Additional Barrier to the Efficient Hydrogenation of Amides and Their Derivatives?
Organometallics ( IF 2.5 ) Pub Date : 2024-01-09 , DOI: 10.1021/acs.organomet.3c00399
James Luk ₁ , Conor L Oates ₁ , José A Fuentes Garcia ₁ , Matthew L Clarke ₁ , Amit Kumar ₁

Affiliation

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.

中文翻译：

酰胺和聚氨酯的锰催化加氢：催化剂抑制是酰胺及其衍生物高效加氢的额外障碍吗？

酰胺和其他具有 N-C═O 官能团的亲电性较低的羰基衍生物的氢化需要显着改进范围和催化活性，才能在工业中成为真正有用的反应。在这里，我们报告了一项研究的结果，该研究检查了作为催化剂抑制剂的含氮化合物（如脂肪胺）是否进一步不利于此类反应。在这种情况下，先前确定的对映体纯锰催化剂在酮、N-芳基亚胺和酯的加氢反应中是有效的，被用作锰催化剂的原型。这是通过用各种含氮化合物掺杂模型酯加氢并监测进度来实现的。在此基础上，描述了酰胺和聚氨酯催化氢化的方案，包括轴向手性酰胺的催化氢化，导致低水平的动力学分辨率。含氮化合物在催化加氢过程中充当抑制剂的假设也通过使用光谱学（高压红外（IR）、核磁共振（NMR））和质谱研究得到了合理化。

更新日期：2024-01-09

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