镧系金属用于有机反应的研究──无水NdCl_3／萘锂体系与酮及异氰酸酯和异硫氰酸酯的反应  

Studies on the Application of Lanthanoid Metalto Organic Reactions──The Reaction of Anhydrous NdCl3/Lithium Naphthalide System with Ketones or Isocyanates or Isothiocyanates

作　　者：包建春[1] 贝浼智[1] 

机构地区：[1]南京师范大学化学系

出　　处：《高等学校化学学报》1995年第6期881-886,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金

摘　　要：报道了无水ＮｄＣｌ３／萘锂体系与二苯酮、α，β－不饱和羰基化合物、异氰酸酯及异硫氰酸酯的反应。研究发现：无水ＮｄＣｌ３／萘锂体系可引发α，β－不饱和羰基化合物发生新奇的二聚环化反应得到互为异构体的环戊醇衍生物，与异氰酸酯或异硫氰酸酯反应则得到较高产率的相应的还原偶联产物草酰胺或硫代草酰胺。而在某些配体存在下，无水ＮｄＣ１３／萘锂体系与二苯酮作用时，有别于单纯的ＮｄＣｌ３／萘锂体系，反应选择性发生了明显的改变，主要得到二苯甲醇。This paper reports the reactions of anhydrous NdCl_3/LiNp(LiNp=Lithium Naphthalide)system with benzoplienone,α,β-unsaturated carbonyl compounds,isocyanates and isothiocyanates, respectively.It is found that the anhydrous NdCl_3/LiNp system can promote a novel cyclodimerization of α,β-unsaturated carbony compound to give(IR,2S,3R,4S)-cyclopentanol derivatives and their stereoisomer.The same system can also react with isocyanates or isothiocyanates to give the corresponding reductive coupling products in good yield.We also found that the new system of NdCl_3/LiNp/Ligand,which differs from the NdCl_3/LiNp system, shows a different selectivity in the reaction with benzophenone to mainly give diphenyl methanol.

关 键 词：萘锂 二苯酮 异氰酸酯 氯化铵 镧系金属 

分 类 号：O614.33[理学—无机化学] O621.254.2[理学—化学]