镧系元素化合物在有机合成中的应用 —————— 酮在LnCl~3 / K 及 K 作用下的反应

本文研究了酮在LnCl~3/K (Ln=Nd,Gd)及K作用下的反应,并发现共轭酮发生还原偶联, 脂肪酮发生羟醛缩合.并给出了可能的机理.     

Anomalous concentration dependence of the coordination behavior of Cl− ion to Ln3+ ion (Ln3+ = rare‐earth ion) in anhydrous LnCl3 alcohol solutions

Raman spectroscopic measurements were carried out for the anhydrous LnCl₃·20ROH·XLiCl solutions (Ln³⁺ = La³⁺− Lu³⁺, X = 0–3; ROH = MeOH, EtOH, n‐PrOH) in the liquid state. The salt concentration (X) dependence of the wavenumber for the Ln–Cl stretching Raman band (ν_Ln–Cl) is examined in conjunction with the formation of chloro‐rare‐earth complexes. We have obtained very intriguing results including the fact that the chloro complexations of the middle rare‐earth ions (e.g. gadolinium, holmium ions, etc.) in the MeOH and EtOH solutions show peculiar behavior with regard to the salt concentration dependence: the ν_Ln–Cl wavenumber increases with the increasing chloride concentration. However, the ν_Ln–Cl wavenumbers of the light and heavy rare‐earth (e.g. lanthanum, lutetium, etc.) salt solutions show normal behavior; i.e. ν_Ln–Cl decreases with the increasing chloride concentration. On the other hand, in the n‐PrOH solutions, the ν_Ln–Cl frequency in the solutions of all the rare‐earth elements exhibits a normal behavior. We now present a possible mechanism for this anomalous concentration dependence of coordination of Cl⁻ ions to Ln³⁺ ions in anhydrous LnCl₃ alcohol solutions. Copyright © 2007 John Wiley & Sons, Ltd.     

Recent Advances in Organic Reactions Catalyzed by Lanthanide(III) Complexes

Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｔｈｅｎａｍｅ“ｒａｒｅｅａｒｔｈ”ａｐｐｌｉｅｓｔｏｔｈｅｌａｎｔｈａｎｉｄｅｓ ,ｙｔｔｒｉｕｍａｎｄｓｃａｎｄｉｕｍ .Ｔｈｅ 15ｅｌｅｍｅｎｔｓｏｆｌａｎｔｈａｎｉｄｅｆｒｏｍｌａｎｔｈａｎｕｍｔｏｌｕｔｅｔｉｕｍｃｏｎｓｔｉｔｕｔｅａｕｎｉｑｕｅｆａｍｉｌｙｏｆｃｌｏｓｅｌｙｒｅｌａｔｅｄｅｌｅｍｅｎｔｓ (ｔｈｅｄｉｆｆｅｒｅｎｃｅｌｙｉｎｇｉｎｔｈｅｎｕｍ ｂｅｒｏｆ 4ｆｅｌｅｔｒｏｎｓ)ｆｒｏｍｗｈｉｃｈｒｅｇｅｎｔｓｏｒｃａｔａｌｙｓｔｓｗｉｔｈ“ｔｕｎａｂ…     

Recent Advances in Organic Reactions Catalyzed by Lanthanide（Ⅲ） Complexes

Lanthanide compounds have been attracting much attention in organic synthesis.Chiral Ln-substituted BINOL have been widely studied in several asymmetric organic reactions.LnCl3 and Ln(OTf)3 have been expected to serve as Lewis acide and have been applied to many important synthetic reactions in a one-pot manner,Ln(O-i-Pr)3 exhibits some basic characters,which also can be utilized in some special organic transformation.This article deals with some lanthanides(Ⅲ）complexes promoted organic reactios,which we have recently developed.