Samarium and a catalytic amount of iodine were used to obtain functionalized cyclopentenes by reductive dimerization followed by intramolecular cyclization of 1， 1-dicyanoalkenes under mild conditions.
The anhydrous NdCl_a-LiNp (LiNp=Lithium uaphthalide) system has been fouud to cause a novel cyclodimerization of α, β-unsaturated ketoues to give cycio- -pentauol derivatives (1 and 2). A possible reaction mechanism...The anhydrous NdCl_a-LiNp (LiNp=Lithium uaphthalide) system has been fouud to cause a novel cyclodimerization of α, β-unsaturated ketoues to give cycio- -pentauol derivatives (1 and 2). A possible reaction mechanism was proposed.展开更多
A series-of lanthanide complexes including (Ind)(3)Sm(THF) (1), [(MeCP)(2)Sm(mu-SPh)(THF)](2),(2), [(MeCp)(2)Y(mu-O-i-Pr)](2) (3), (MeCp)(3)Sm.THF (4), Sm(SPh)(3) (hmpa)(3) (5), [(MeCp)(2)Y(mu-OCH2CF3)](2) (6) and (CF...A series-of lanthanide complexes including (Ind)(3)Sm(THF) (1), [(MeCP)(2)Sm(mu-SPh)(THF)](2),(2), [(MeCp)(2)Y(mu-O-i-Pr)](2) (3), (MeCp)(3)Sm.THF (4), Sm(SPh)(3) (hmpa)(3) (5), [(MeCp)(2)Y(mu-OCH2CF3)](2) (6) and (CF3CH2O)(3)Y(THF)(3) (7) were synthesized and they have good activity for the oligomerization of phenyl isocyanate. Among-them 5 shows,the highest activity. The conversion is as high as 96.2%, with 1/2500 of the molar ratio of cat. / PhNCO. The main components in oligomer were characterized to be a cyclodimer and a cyclotrimer. The ratio of cyclodimer,to cyclotrimer depends on the lanthanide complexes:used. 7 gave 85.2% cyclotrimer with 1/300 of the molar ratio of cat./PhNCO at 40 V for 0.5 h, while 5 gave 77.6% cyclodimer with 1/300 of the molar ratio of cat. /PhNCO at 40 degreesC for 4 h.展开更多
A series of poly(ethylene glycol) biscoumarinyloxyacetates have been synthesized and their intramolecular photochemical cyclodimerizations have been studied.It was found that only syn-HT configuration products were ob...A series of poly(ethylene glycol) biscoumarinyloxyacetates have been synthesized and their intramolecular photochemical cyclodimerizations have been studied.It was found that only syn-HT configuration products were obtained when these bisesters were directly irradiated in chloroform,and the yields of the products decreased with the increase of the chain length.This photocyclization reaction is a convenient and effective method to synthesize macrocyclic compounds.展开更多
A series of polymethylenediamine bis(4-methyl-7-coumarinyl)oxyacetic amides have been synthesized and their intramolecular photochemical cyclodimerizations have been investigated. It was found that only syn-HT configu...A series of polymethylenediamine bis(4-methyl-7-coumarinyl)oxyacetic amides have been synthesized and their intramolecular photochemical cyclodimerizations have been investigated. It was found that only syn-HT configuration products were obtained when these bisamides were directly irradiated in dimethyl sulfoxide solution and the yields of the products decreased with the increase of the chain length. The structures of long chain amides and their intramolecular photocyclization products were determined by IR, MS, 1H NMR and elemental analysis.展开更多
基金Preject (No. 20072033) supported by the National Natural Science Foundation of China and Zhejiang Provincial Natural Science Foundation of China
文摘Samarium and a catalytic amount of iodine were used to obtain functionalized cyclopentenes by reductive dimerization followed by intramolecular cyclization of 1， 1-dicyanoalkenes under mild conditions.
基金Project supported by the National Science Foundation of China
文摘The anhydrous NdCl_a-LiNp (LiNp=Lithium uaphthalide) system has been fouud to cause a novel cyclodimerization of α, β-unsaturated ketoues to give cycio- -pentauol derivatives (1 and 2). A possible reaction mechanism was proposed.
文摘A series-of lanthanide complexes including (Ind)(3)Sm(THF) (1), [(MeCP)(2)Sm(mu-SPh)(THF)](2),(2), [(MeCp)(2)Y(mu-O-i-Pr)](2) (3), (MeCp)(3)Sm.THF (4), Sm(SPh)(3) (hmpa)(3) (5), [(MeCp)(2)Y(mu-OCH2CF3)](2) (6) and (CF3CH2O)(3)Y(THF)(3) (7) were synthesized and they have good activity for the oligomerization of phenyl isocyanate. Among-them 5 shows,the highest activity. The conversion is as high as 96.2%, with 1/2500 of the molar ratio of cat. / PhNCO. The main components in oligomer were characterized to be a cyclodimer and a cyclotrimer. The ratio of cyclodimer,to cyclotrimer depends on the lanthanide complexes:used. 7 gave 85.2% cyclotrimer with 1/300 of the molar ratio of cat./PhNCO at 40 V for 0.5 h, while 5 gave 77.6% cyclodimer with 1/300 of the molar ratio of cat. /PhNCO at 40 degreesC for 4 h.
基金Project supported by the National Natural Science Foundation of China.
文摘A series of poly(ethylene glycol) biscoumarinyloxyacetates have been synthesized and their intramolecular photochemical cyclodimerizations have been studied.It was found that only syn-HT configuration products were obtained when these bisesters were directly irradiated in chloroform,and the yields of the products decreased with the increase of the chain length.This photocyclization reaction is a convenient and effective method to synthesize macrocyclic compounds.
文摘A series of polymethylenediamine bis(4-methyl-7-coumarinyl)oxyacetic amides have been synthesized and their intramolecular photochemical cyclodimerizations have been investigated. It was found that only syn-HT configuration products were obtained when these bisamides were directly irradiated in dimethyl sulfoxide solution and the yields of the products decreased with the increase of the chain length. The structures of long chain amides and their intramolecular photocyclization products were determined by IR, MS, 1H NMR and elemental analysis.
