Design of Manganese Phenol Pi‐complexes as Shvo‐type Catalysts for Transfer Hydrogenation of Ketones,ChemCatChem

当前位置： X-MOL 学术 › ChemCatChem › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Design of Manganese Phenol Pi‐complexes as Shvo‐type Catalysts for Transfer Hydrogenation of Ketones
ChemCatChem ( IF 3.8 ) Pub Date : 2019-02-27 , DOI: 10.1002/cctc.201801797
Nikita V. Shvydkiy ₁ , Oleksandr Vyhivskyi ₂ , Yulia V. Nelyubina ₁ , Dmitry S. Perekalin _{1,

3}

Affiliation

Catalytic hydrogenation is one of the most important reactions both in academic research and industry. We explored ability of the manganese pi‐complexes to act as Shvo‐type catalysts for transfer hydrogenation of ketones. DFT calculations suggested that the transfer of hydrogen atoms from the hypothetical intermediate [(C₆Me₃H₂OH)Mn(CO)₂H] to acetone has low activation barrier of 10.9 kcal mol⁻¹. Experimentally a number of ketones with various functional groups (OMe, NH₂, Cl, CF₃, pyridyl) were successfully reduced in isopropanol at 90 °C in the presence of the complex [(C₆Me₃H₂OH)Mn(CO)₃]BF₄ (1 mol %) and ^tBuOK (75 mol %). However, further investigation revealed that the reduction was mainly promoted by base rather than the manganese complex.

中文翻译：

锰苯酚Pi配合物作为SHVO型酮转移加氢催化剂的设计

催化加氢是学术研究和工业中最重要的反应之一。我们探索了锰pi-络合物作为Shvo型催化剂进行酮转移加氢的能力。DFT计算表明，从假设的中间体[（C ₆ Me ₃ H ₂ OH）Mn（CO）₂ H]到丙酮的氢原子转移具有较低的10.9 kcal mol ^-1活化势垒。在有配合物[（C ₆ Me ₃ H _2）的存在下，在90°C的异丙醇中，实验成功地在异丙醇中成功还原了具有各种官能团（OMe，NH ₂，Cl，CF ₃，吡啶基）的许多酮。OH）Mn（CO）₃ ] BF ₄（1摩尔％）和^t BuOK（75摩尔％）。但是，进一步的调查表明，还原主要是由碱而不是锰配合物促进的。

更新日期：2019-02-27

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南