Michael addition of nitroalkanes to α,β-unsaturated carbonyl compounds occurs in the presence of KF/AI_2O_3/PEG4000 without solvent.Yields are fair to good and work-ups are easy.
In the presence of CrC13 /Fe bimetal couple,per(poly)fluoroalkyl iodides add to vinyl cyclopropane compounds giving addition-ring-opening products in good yields.
The selectivity of organosamarium(Ⅲ) hydride in reducing unsaturated carbonyl compounds has been studied. Dimeric organosamarium hydride[(C_9H_7)_2SmH]_2·4THF·NaCl prepared by the reaction of (C_9H_7)_2SmCl...The selectivity of organosamarium(Ⅲ) hydride in reducing unsaturated carbonyl compounds has been studied. Dimeric organosamarium hydride[(C_9H_7)_2SmH]_2·4THF·NaCl prepared by the reaction of (C_9H_7)_2SmCl·2THF with NaH in THF reacts with unsaturated carbonyl compounds to give the corresponding reduction products with a high selectivity. The carbonyl groups have been reduced while the carbon-carbon double bonds are not affected.展开更多
Selective hydrogenation of the carbonyl bond inα,β-unsaturated carbonyl compounds is rather challenging owing to the more feasible hydrogenation of ethylenic bond from both thermodynamic and kinetic aspects.Here,we ...Selective hydrogenation of the carbonyl bond inα,β-unsaturated carbonyl compounds is rather challenging owing to the more feasible hydrogenation of ethylenic bond from both thermodynamic and kinetic aspects.Here,we demonstrate a facile emulsionbased molecule-nanoparticle self-assembly strategy for the atomic engineering of Ir species on three-dimensional CeO_(2)spheres(Ir1@CeO_(2)).When applied to the hydrogenation ofα,β-unsaturated aldehydes,Ir1@CeO_(2)catalyst remarkably exhibited~100%selectivity towards unsaturated alcohols,whereas the formation of Ir nanoparticles on CeO_(2)drastically decreased the selectivity for unsaturated alcohols.Spectroscopic studies revealed that strong metal-support interactions triggered the charge transfer from Ir to CeO_(2),leading to the partial reduction of Ce^(4+)to Ce^(3+)along with the formation new Ir^(δ+)-O_(2)--Ce^(3+)(OV)interfaces.The electrophilic atomic Ir species at the Ir^(δ+)-O_(2)--Ce^(3+)(OV)interfaces would therefore preferentially adsorb and facilitate hydrogenation of polar C=O bond to achieve exceptional selectivity.展开更多
文摘Michael addition of nitroalkanes to α,β-unsaturated carbonyl compounds occurs in the presence of KF/AI_2O_3/PEG4000 without solvent.Yields are fair to good and work-ups are easy.
文摘In the presence of CrC13 /Fe bimetal couple,per(poly)fluoroalkyl iodides add to vinyl cyclopropane compounds giving addition-ring-opening products in good yields.
文摘The selectivity of organosamarium(Ⅲ) hydride in reducing unsaturated carbonyl compounds has been studied. Dimeric organosamarium hydride[(C_9H_7)_2SmH]_2·4THF·NaCl prepared by the reaction of (C_9H_7)_2SmCl·2THF with NaH in THF reacts with unsaturated carbonyl compounds to give the corresponding reduction products with a high selectivity. The carbonyl groups have been reduced while the carbon-carbon double bonds are not affected.
基金the National Natural Science Foundation of China(No.21901007)the Natural Science Foundation of Anhui Province(No.2008085QB83)+1 种基金the Science and Technology Development Fund(FDCT)of Macao SAR(No.0032/2021/ITP)the University of Macao(No.MYRG2020-00026-FST)。
文摘Selective hydrogenation of the carbonyl bond inα,β-unsaturated carbonyl compounds is rather challenging owing to the more feasible hydrogenation of ethylenic bond from both thermodynamic and kinetic aspects.Here,we demonstrate a facile emulsionbased molecule-nanoparticle self-assembly strategy for the atomic engineering of Ir species on three-dimensional CeO_(2)spheres(Ir1@CeO_(2)).When applied to the hydrogenation ofα,β-unsaturated aldehydes,Ir1@CeO_(2)catalyst remarkably exhibited~100%selectivity towards unsaturated alcohols,whereas the formation of Ir nanoparticles on CeO_(2)drastically decreased the selectivity for unsaturated alcohols.Spectroscopic studies revealed that strong metal-support interactions triggered the charge transfer from Ir to CeO_(2),leading to the partial reduction of Ce^(4+)to Ce^(3+)along with the formation new Ir^(δ+)-O_(2)--Ce^(3+)(OV)interfaces.The electrophilic atomic Ir species at the Ir^(δ+)-O_(2)--Ce^(3+)(OV)interfaces would therefore preferentially adsorb and facilitate hydrogenation of polar C=O bond to achieve exceptional selectivity.