A catalyst composed of commercially available Zn(OAc)₂ and 1,10-phenanthroline (phen) was effective in the N-formylation/N-methylation of amines using CO₂ as the C1 source in the presence of hydrosilanes. An equimolar reaction of N-methylaniline with PhSiH₃ under a CO₂ atmosphere yielded the N-formylation product in 92% yield at 25 °C. Scale-up of the reaction using 10 mmol substrate was also successful in affording the desired product in 83% yield (1.1 g). This catalyst exhibits a high thermal stability and a turnover number (TON) of 385 000 at 150 °C. In addition, the reaction of N-methylaniline in the presence of excess Ph₂SiH₂ produced N,N-dimethylaniline. Furthermore, our catalytic protocol was developed for the N-formylation of amides and carbamates, which have smaller pK_a values and lower reactivities than the corresponding amines. The present Zn(OAc)₂/phen catalyst was found to show versatility in the conversion of CO₂ and amines into several functionalized organic chemicals under mild conditions. We propose that the basic counter anion (i.e., the acetate) of the catalyst activates both the Si–H and N–H bonds.

中文翻译：

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胺与二氧化碳和氢硅烷的选择性N-甲酰化/ N-甲基化以及酰胺和氨基甲酸酯的N-甲酰化：促进锌催化剂的基本抗衡阴离子

由市售的Zn（OAc）₂和1,10-菲咯啉（phen）组成的催化剂在存在氢硅烷的情况下，使用CO ₂作为C1源，对胺的N-甲酰化/ N-甲基化反应有效。N-甲基苯胺与PhSiH ₃在CO ₂气氛下的等摩尔反应在25°C下以92％的收率得到N-甲酰化产物。使用10 mmol底物扩大反应规模也成功获得了所需的产物，收率为83％（1.1 g）。该催化剂表现出高的热稳定性，在150°C下的转化率（TON）为385,000。另外，N的反应-甲基苯胺在过量的Ph ₂ SiH ₂存在下产生N，N-二甲基苯胺。此外，我们开发了用于酰胺和氨基甲酸酯的N-甲酰化的催化方案，与相应的胺相比，它们具有更小的p K _a值和更低的反应性。发现本发明的Zn（OAc）₂ / phen催化剂在温和的条件下在将CO ₂和胺转化为几种官能化的有机化学品中显示出多功能性。我们建议催化剂的基本抗衡阴离子（即乙酸根）激活Si-H和N-H键。