| 摘要： |
Allylic alcohols are the essential building blocks widely used in diverse streams of organic inventions for pharmaceuticals, fragrances, agrochemicals and polymers. Currently, allylic alcohols are industrially produced from petroleum-based feedstocks via atom uneconomic processes. More sustainable synthesis route for allylic alcohols is limited. Herein, a methodology for the direct and highly selective production of allylic alcohols has been accomplished by controlled dehydrogenative a-methylenation of alcohols with methanol. This transformation is enabled by interfacial Lewis acid-basic pair on tailor-made ZnO/4Mg1ZrO(x) mixed oxide. High selectivity (83 similar to 92%) of allylic alcohols is the consequence of alcohols acceptorless dehydrogenation to liberation of H-2 and Meerwein-Ponndorf-Verley type hydrogen transfer onto C=O bonds of unsaturated aldehydes. Furthermore, the prepared ZnO/4Mg1ZrO(x) mixed oxide shows good stability after 200 h time on stream test. These observations could additionally allow us to design multifunctional solid acid-basic catalysts for the transformations of renewable oxygenates into value-added chemicals. |
