We have designed and prepared β-cyclodextrin （β-CD）-functionalized multi-walled nanotubes （MWCNTs-g-CD） for the oxidation of cinnamon oil to natural benzaldehyde under aqueous condi- tions. The synergistic effec...We have designed and prepared β-cyclodextrin （β-CD）-functionalized multi-walled nanotubes （MWCNTs-g-CD） for the oxidation of cinnamon oil to natural benzaldehyde under aqueous condi- tions. The synergistic effect of combining MWCNTs with β-CD led to a remarkable increase in the performance of the MWCNTs-g-CD for the catalytic oxidation of cinnamaldehyde, which exhibited 95% cinnamaldehyde conversion and 85% selectivity to natural benzaldehyde with a short reaction time of 10 rain. The MWCNTs-g-CD also exhibited outstanding recyclability with good stability, showing no discernible decrease in their catalytic activity over five reaction cycles.展开更多
Nineβ‐cyclodextrin derivatives containing an amino group were synthesized via nucleophilic sub‐stitution from mono（6‐O‐p‐tolylsulfonyl）‐β‐cyclodextrin and used in asymmetric biomimetic Mi‐chael addition re...Nineβ‐cyclodextrin derivatives containing an amino group were synthesized via nucleophilic sub‐stitution from mono（6‐O‐p‐tolylsulfonyl）‐β‐cyclodextrin and used in asymmetric biomimetic Mi‐chael addition reactions in water at room temperature. The mechanism responsible for the moder‐ate activity and enantioselectivity of the β‐cyclodextrin derivatives was explored using nuclear magnetic resonance spectroscopy, namely 2D 1H rotating‐frame overhauser effect spectroscopy （ROESY）, ultraviolet absorption spectroscopy, and quantum chemical calculations, which provide a useful technique for investigating the formation of inclusion complexes. The effects of the pH of the reaction medium, theβ‐cyclodextrin derivative dosage, the structure of the modifying amino group, and various substrates on the yield and enantioselectivity were investigated. The results indicated that these factors had an important effect on the enantiomeric excess （ee） in the reaction system. Experiments using a competitor for inclusion complex formation showed that a hydrophobic cavity is necessary for enantioselective Michael addition. A comparison of the reactions using 4‐nitro‐β‐nitrostyrene and 2‐nitro‐β‐nitrostyrene showed that steric hindrance improved the enan‐tioselectivity. This was verified by the optimized geometries obtained from quantum chemical cal‐culations. An ee of 71%was obtained in the asymmetric Michael addition of cyclohexanone and 2‐nitro‐β‐nitrostyrene, using （S）‐2‐aminomethylpyrrolidine‐modified β‐CD as the catalyst, in an aqueous buffer solution, i.e., CH3COONa‐HCl （pH 7.5）.展开更多
基金supported by the National Natural Science Foundation of China (21376279, 21276102, 21425627)Guangdong Technology Research Center for Synthesis and Separation of Thermosensitive Chemicals (2015B090903061)+1 种基金the Fundamental Research Funds for the Central Universities (14lgpy28)Guangzhou Science and Technology Plan Projects (2014J4100125)~~
文摘We have designed and prepared β-cyclodextrin （β-CD）-functionalized multi-walled nanotubes （MWCNTs-g-CD） for the oxidation of cinnamon oil to natural benzaldehyde under aqueous condi- tions. The synergistic effect of combining MWCNTs with β-CD led to a remarkable increase in the performance of the MWCNTs-g-CD for the catalytic oxidation of cinnamaldehyde, which exhibited 95% cinnamaldehyde conversion and 85% selectivity to natural benzaldehyde with a short reaction time of 10 rain. The MWCNTs-g-CD also exhibited outstanding recyclability with good stability, showing no discernible decrease in their catalytic activity over five reaction cycles.
基金supported by the the National Natural Science Foundation of China (21376279, 21176268, 21036009)the Science and Technology Major Program of Guangdong Province (2012A080103005)Special Project on Integration of Production, Education And Research of Guangdong Province (2011B090400439)~~
基金supported by the National Natural Science Foundation of China (21425627,21376279)~~
文摘Nineβ‐cyclodextrin derivatives containing an amino group were synthesized via nucleophilic sub‐stitution from mono（6‐O‐p‐tolylsulfonyl）‐β‐cyclodextrin and used in asymmetric biomimetic Mi‐chael addition reactions in water at room temperature. The mechanism responsible for the moder‐ate activity and enantioselectivity of the β‐cyclodextrin derivatives was explored using nuclear magnetic resonance spectroscopy, namely 2D 1H rotating‐frame overhauser effect spectroscopy （ROESY）, ultraviolet absorption spectroscopy, and quantum chemical calculations, which provide a useful technique for investigating the formation of inclusion complexes. The effects of the pH of the reaction medium, theβ‐cyclodextrin derivative dosage, the structure of the modifying amino group, and various substrates on the yield and enantioselectivity were investigated. The results indicated that these factors had an important effect on the enantiomeric excess （ee） in the reaction system. Experiments using a competitor for inclusion complex formation showed that a hydrophobic cavity is necessary for enantioselective Michael addition. A comparison of the reactions using 4‐nitro‐β‐nitrostyrene and 2‐nitro‐β‐nitrostyrene showed that steric hindrance improved the enan‐tioselectivity. This was verified by the optimized geometries obtained from quantum chemical cal‐culations. An ee of 71%was obtained in the asymmetric Michael addition of cyclohexanone and 2‐nitro‐β‐nitrostyrene, using （S）‐2‐aminomethylpyrrolidine‐modified β‐CD as the catalyst, in an aqueous buffer solution, i.e., CH3COONa‐HCl （pH 7.5）.
