Fluoride‐Catalyzed Methylation of Amines by Reductive Functionalization of CO2 with Hydrosilanes
作者： Xiao-Fang Liu , Ran Ma , Chang Qiao , Han Cao , Liang-Nian He
关键词: Organocatalysis 、 Formamides 、 Methylamines 、 Organic chemistry 、 Triethoxysilane 、 Chemistry 、 Formylation 、 Deoxygenation 、 Phenylsilane 、 Chemoselectivity
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 different substituents show discriminatory reducing activity. Thus, formation further reduction products, that is, could be controlled elegantly tuning hydrosilane types. Formamides were obtained exclusively under an atmospheric pressure triethoxysilane. Using phenylsilane as a reductant, attained up 99 % yield at 50 °C coupled complete deoxygenation CO2. The crucial intermediate silyl formate in formylation step identified thereby tentative mechanism involving fluoride-promoted hydride transfer from CO2/formamide proposed. Striking features this metal-free protocol are methylation hydrosilanes mild reaction conditions.
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