Rational design of active sites is essential for catalysts to obtain high activity and selectivity in organic synthesis. However, formation of uniform active sites over heterogeneous catalysts is generally difficult, and development of a new methodology for fine tuning of the active sites over heterogeneous catalysts is highly required. Modification of heterogeneous catalysts with organic modifiers such as self-assembled monolayer (SAM) attracts is one promissing method [1], but modification of metal oxides with organic modifiers is quite rare in spite of metal oxides being durable and stable for heating, and widely used as acid/base catalysts in industry. Herein, we found that the heterogeneous and homogeneous hybrid catalyst composed of CeO2 and 2-cyanopyridine was effective for base-catalyzed organic reactions such as hydromethoxylation of acrylonitrile [2,3], transesterification [2], Knoevenagel condensation [2], carbonate derivative synthesis from CO2 such as carbonates, carbamates, ureas and polycarbonates [4]. The hybrid catalyst of CeO2 and 2-cyanopyridine showed about 2000-fold higher activity than CeO2 in the hydromethoxylation of acrylonitrile. The basicity over the hybrid catalyst of CeO2 and 2-cyanopyridine was much higher than that over CeO2 by a factor of 109, and the pKa (in CH3CN) was estimated to be ∼21, which puts it in the superbase category. In this talk, I will introduce the catalysis of the hybrid catalyst composed of CeO2 and nitriles.

Heterogeneous and homogeneous hybrid catalyst of CeO2 and nitriles ~strong base catalyst~

2019 Fall National Meeting

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