Photopromoted carbonylation of alkyl bromides with carbon monoxide or carbon dioxide catalyzed by copper salts can be carried out under ambient conditions （atmospheric pressure and room temperature） and the correspo...Photopromoted carbonylation of alkyl bromides with carbon monoxide or carbon dioxide catalyzed by copper salts can be carried out under ambient conditions （atmospheric pressure and room temperature） and the corresponding ester was produced. The yield and the selectivity of the ester can be improved greatly by addition of sodium phosphate.展开更多
The photopromoted carbonylation of chloroalkanes with carbon monoxide catalyzed by cobalt compounds[Co（OAc）2,CoCl2] in the presence of KI was carried out under ambient conditions.The results revealed that the cataly...The photopromoted carbonylation of chloroalkanes with carbon monoxide catalyzed by cobalt compounds[Co（OAc）2,CoCl2] in the presence of KI was carried out under ambient conditions.The results revealed that the catalytic activity of Co（OAc）2 was higher than that of CoCl2.A basic additive NaOAc was beneficial to the reaction.Interestingly,with NaOAc as an additive, Co（OAc）2 and CoCl2 exhibited similar catalytic activity.Preliminary work showed that the role of iodide ion was initially to form active iodoalkanes via substituting chloride ion in chloroalkanes in situ,and then,the carbonylation of iodoalkanes proceeded under irradiation.展开更多
The carbonylation of phenyl bromide catalyzed by Co（OAc）_2 has been investigated with PhCOPh as a sensitizer under visible light in the presence of basic additive.With strong base CH_3ONa,PhCOOCH_3 is produced in 70...The carbonylation of phenyl bromide catalyzed by Co（OAc）_2 has been investigated with PhCOPh as a sensitizer under visible light in the presence of basic additive.With strong base CH_3ONa,PhCOOCH_3 is produced in 70%yield with 100%selectivity,the similar results are also obtained with a stronger base（CH_3）_3CONa.However,with another strong base NaOH,the yield of the ester is only 40%.On the other hand,with weak base NaOAc or（n-C_4H_9）_3N,phenyl bromide cannot be carbonylated.The results of carbonylation of the six substituted phenyl bromides suggest that the activities of o,m,p-BrC_6H_4CH_3 are similar to phenyl bromide, while the activities of o,m,p-BrC_6H_4Cl are higher with the high yields（≥93%） of the corresponding chloro-esters.In addition,the relative position of bromine and chlorine or methyl on phenyl ring has little effect on the activity of the carbonylation.展开更多
基金the National Natural Science Foundation of China(No.20372012)for the generous financial support.
文摘Photopromoted carbonylation of alkyl bromides with carbon monoxide or carbon dioxide catalyzed by copper salts can be carried out under ambient conditions （atmospheric pressure and room temperature） and the corresponding ester was produced. The yield and the selectivity of the ester can be improved greatly by addition of sodium phosphate.
文摘The photopromoted carbonylation of chloroalkanes with carbon monoxide catalyzed by cobalt compounds[Co（OAc）2,CoCl2] in the presence of KI was carried out under ambient conditions.The results revealed that the catalytic activity of Co（OAc）2 was higher than that of CoCl2.A basic additive NaOAc was beneficial to the reaction.Interestingly,with NaOAc as an additive, Co（OAc）2 and CoCl2 exhibited similar catalytic activity.Preliminary work showed that the role of iodide ion was initially to form active iodoalkanes via substituting chloride ion in chloroalkanes in situ,and then,the carbonylation of iodoalkanes proceeded under irradiation.
文摘The carbonylation of phenyl bromide catalyzed by Co（OAc）_2 has been investigated with PhCOPh as a sensitizer under visible light in the presence of basic additive.With strong base CH_3ONa,PhCOOCH_3 is produced in 70%yield with 100%selectivity,the similar results are also obtained with a stronger base（CH_3）_3CONa.However,with another strong base NaOH,the yield of the ester is only 40%.On the other hand,with weak base NaOAc or（n-C_4H_9）_3N,phenyl bromide cannot be carbonylated.The results of carbonylation of the six substituted phenyl bromides suggest that the activities of o,m,p-BrC_6H_4CH_3 are similar to phenyl bromide, while the activities of o,m,p-BrC_6H_4Cl are higher with the high yields（≥93%） of the corresponding chloro-esters.In addition,the relative position of bromine and chlorine or methyl on phenyl ring has little effect on the activity of the carbonylation.
