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Benzimidazole fragment containing Mn-complex catalyzed hydrosilylation of ketones and nitriles
Tetrahedron ( IF 2.1 ) Pub Date : 2020-07-30 , DOI: 10.1016/j.tet.2020.131439
Kasturi Ganguli , Adarsha Mandal , Bidisha Sarkar , Sabuj Kundu

The synthesis of a new bidentate (NN)–Mn(I) complex is reported and its catalytic activity towards the reduction of ketones and nitriles is studied. On comparing the reactivity of various other Mn(I) complexes supported by benzimidazole ligand, it was observed that the Mn(I) complexes bearing 6-methylpyridine and benzimidazole fragments exhibited the highest catalytic activity towards monohydrosilylation of ketones and dihydrosilylation of nitriles. Using this protocol, a wide range of ketones were selectively reduced to the corresponding silyl ethers. In case of unsaturated ketones, the chemoselective reduction of carbonyl group over olefinic bonds was observed. Additionally, selective dihydrosilylation of several nitriles were also achieved using this complex. Mechanistic investigations with radical scavengers suggested the involvement of radical species during the catalytic reaction. Stoichiometric reaction of the Mn(I) complex with phenylsilane revealed the formation of a new Mn(I) complex.



中文翻译:

含锰配合物的苯并咪唑片段催化酮和腈的氢化硅烷化

报道了一种新的双齿(NN)-Mn(I)配合物的合成,并研究了其对酮和腈还原的催化活性。在比较苯并咪唑配体负载的其他各种Mn(I)配合物的反应性时,观察到带有6-甲基吡啶和苯并咪唑片段的Mn(I)配合物对酮的单氢化硅烷化和腈的二氢化硅烷化表现出最高的催化活性。使用该方案,将广泛的酮选择性地还原为相应的甲硅烷基醚。在不饱和酮的情况下,观察到羰基在烯烃键上的化学选择性还原。另外,使用该配合物还实现了几个腈的选择性二氢硅烷化。用自由基清除剂进行的机械研究表明,在催化反应过程中自由基种类的参与。Mn(I)配合物与苯基硅烷的化学计量反应揭示了新的Mn(I)配合物的形成。

更新日期:2020-08-24
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