Acid-catalyzed dehydration of alcohols has been widely employed for the synthesis of alkenes. However, activated alcohols when employed as substrates in dehydration reactions are often pla-gued by the lack of alkene s...Acid-catalyzed dehydration of alcohols has been widely employed for the synthesis of alkenes. However, activated alcohols when employed as substrates in dehydration reactions are often pla-gued by the lack of alkene selectivity. In this work, the reaction system can be significantly improved through enhancing the performance of Lewis acid catalysts in the dehydration of activated alcohols by combining with a Lewis base. Observations of the reaction mechanism revealed that the Lewis base component might have changed the reaction rate order. Although both the principal and side reaction rates decreased, the effect was markedly more observed on the latter reaction. Therefore, the selectivity of the dehydration reaction was improved. On the basis of this observation, a new route to synthesize 2-cinnamyl-1,3-dicarbonyl compounds was developed by using 2-aryl-3,4- di-hydropyran as a starting substrate in the presence of a Lewis acid/Lewis base combined catalyst system.展开更多
A facile and efficient procedure has been developed systematically for the oxidative cleavage of cinna-maldehyde to benzaldehyde by sodium hypochlorite with water as the only solvent in the presence of β-cyclodextrin...A facile and efficient procedure has been developed systematically for the oxidative cleavage of cinna-maldehyde to benzaldehyde by sodium hypochlorite with water as the only solvent in the presence of β-cyclodextrin （abbreviated as β-CD）. Different factors influencing cinnamaldehyde oxidation e.g. reaction temperature, the amount of catalyst and oxidant, have been investigated. The yield of benzaldehyde reaches 76% under the optimum conditions （333 K, 4 h, molar ratio of cinnamaldehyde to β-CD is 1：1）. Furthermore, a feasible reaction mecha-nism including the formation of benzaldehyde and the two main byproducts （phenylacetaldehyde and epoxide of cinnamaldehyde） has been proposed.展开更多
基金supported by the National Natural Science Foundation of China (21173089 and 21373093)the Fundamental Research Funds for the Central Universities of China (2014ZZGH019)the Cooperative Innovation Center of Hubei Province
文摘Acid-catalyzed dehydration of alcohols has been widely employed for the synthesis of alkenes. However, activated alcohols when employed as substrates in dehydration reactions are often pla-gued by the lack of alkene selectivity. In this work, the reaction system can be significantly improved through enhancing the performance of Lewis acid catalysts in the dehydration of activated alcohols by combining with a Lewis base. Observations of the reaction mechanism revealed that the Lewis base component might have changed the reaction rate order. Although both the principal and side reaction rates decreased, the effect was markedly more observed on the latter reaction. Therefore, the selectivity of the dehydration reaction was improved. On the basis of this observation, a new route to synthesize 2-cinnamyl-1,3-dicarbonyl compounds was developed by using 2-aryl-3,4- di-hydropyran as a starting substrate in the presence of a Lewis acid/Lewis base combined catalyst system.
基金Supported by the National＇Natural Science Foundation of China （21036009, 21176268）, the Higher-level Talent Project tor Guangdong Provincial Universities and the Fundamental.Research Funds for the Central Universities.
文摘A facile and efficient procedure has been developed systematically for the oxidative cleavage of cinna-maldehyde to benzaldehyde by sodium hypochlorite with water as the only solvent in the presence of β-cyclodextrin （abbreviated as β-CD）. Different factors influencing cinnamaldehyde oxidation e.g. reaction temperature, the amount of catalyst and oxidant, have been investigated. The yield of benzaldehyde reaches 76% under the optimum conditions （333 K, 4 h, molar ratio of cinnamaldehyde to β-CD is 1：1）. Furthermore, a feasible reaction mecha-nism including the formation of benzaldehyde and the two main byproducts （phenylacetaldehyde and epoxide of cinnamaldehyde） has been proposed.
