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首页> 外文期刊>Chemistry: A European journal >Fluoride-Catalyzed Methylation of Amines by Reductive Functionalization of CO2 with Hydrosilanes
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Fluoride-Catalyzed Methylation of Amines by Reductive Functionalization of CO2 with Hydrosilanes

机译：通过氢硅烷对CO2的还原功能化，氟化物催化胺的甲基化

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摘要

An effective and inexpensive organocatalyst tetrabutylammonium fluoride (TBAF) was developed for the reductive functionalization of CO2 with amines to selectively afford formamides or methylamines by employing hydrosilanes. Hydrosilanes with different substituents show discriminatory reducing activity. Thus, the formation of formamides and further reduction products, that is, methylamines could be controlled by elegantly tuning hydrosilane types. Formamides were obtained exclusively under an atmospheric pressure of CO2 with triethoxysilane. Using phenylsilane as a reductant, methylamines were attained with up to 99% yield at 50 degrees C coupled to a complete deoxygenation of CO2. The crucial intermediate silyl formate in the formylation step was identified and thereby a tentative mechanism involving the fluoride-promoted hydride transfer from the hydrosilane to CO2/formamide was proposed. Striking features of this metal-free protocol are formylation and methylation of amines by reductive functionalization of CO2 with hydrosilanes and mild reaction conditions.
机译：开发了一种有效且廉价的有机催化剂四丁基氟化铵（TBAF），用于通过胺将CO2与胺还原功能化，从而通过使用氢化硅烷选择性地提供甲酰胺或甲胺。具有不同取代基的氢硅烷显示出有区别的还原活性。因此，可以通过优雅地调节氢化硅烷的类型来控制甲酰胺和其他还原产物的形成，即甲胺。甲酰胺仅在CO2的大气压下与三乙氧基硅烷一起获得。使用苯基硅烷作为还原剂，可在50摄氏度下以高达99％的收率获得甲胺，同时完成CO2的完全脱氧。确定了甲酰化步骤中的关键中间体甲硅烷基甲酸酯，并由此提出了一种试探性机理，涉及氟化物促进的氢化物从氢硅烷向CO2 /甲酰胺的转移。该无金属方案的显着特征是通过使用氢硅烷和温和的反应条件对CO2进行还原功能化，可以实现胺的甲酰化和甲基化。

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