3378-71-0Relevant articles and documents
An improved reduction procedure in the synthesis of substituted pyrrolidines via an aminomercuration/reduction sequence of primary alkenylamines
Roubaud, Valerie,Le Moigne, Francois,Mercier, Anne,Tordo, Paul
, p. 1507 - 1516 (1996)
Aminomercuration/reduction sequence of δ-alkenylamines is a typical route to substituted pyrrolidines. Backward reaction to the starting material is a major drawback which occurs during sodium borohydride reduction of the intermediate organomercurial. We describe here a new reduction procedure which prevents almost completely this backward reaction and leads to significant increases in the yields of pyrrolidines.
Reactivity of functionalized indoles with rare-earth metal amides. Synthesis, characterization and catalytic activity of rare-earth metal complexes incorporating indolyl ligands
Feng, Zhijun,Wei, Yun,Zhou, Shuangliu,Zhang, Guangchao,Zhu, Xiancui,Guo, Liping,Wang, Shaowu,Mu, Xiaolong
, p. 20502 - 20513 (2015/12/05)
The reactivity of several functionalized indoles 2-(RNHCH2)C8H5NH (R = C6H5 (1), tBu (2), 2,6-iPr2C6H3 (3)) with rare-earth metal amides is described. Reactions of 1 or 2 with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 (RE = Eu, Yb) respectively produced the europium complexes [2-(C6H5NCH)C8H5N]2Eu[N(SiMe3)2] (4) and [2-(tBuNCH)C8H5N]Eu[N(SiMe3)2]2 (5), and the ytterbium complex [2-(tBuNCH)C8H5N]2Yb[N(SiMe3)2] (6), containing bidentate anionic indolyl ligands via dehydrogenation of the amine to the imine. In contrast, reactions of the more sterically bulky indole 3 with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 afforded complexes [2-(2,6-iPr2C6H3NCH2)C8H5N]RE[N(SiMe3)2](THF)2 (RE = Yb (7), Y (8), Er (9), Dy (10)) with the deprotonated indolyl ligand. While reactions of 3 with yttrium and ytterbium amides in refluxing toluene respectively gave the complexes [2-(2,6-iPr2C6H3NCH)C8H5N]3Y (11) and [2-(2,6-iPr2C6H3NCH)C8H5N]2YbII(THF)2 (12), along with transformation of the amino group to the imino group, and also with a reduction of Yb3+ to Yb2+ in the formation of 12. Reactions of 3 with samarium and neodymium amides provided novel dinuclear complexes {[μ-η5:η1:η1-2-(2,6-iPr2C6H3NCH2)C8H5N]RE[N(SiMe3)2]}2 (RE = Sm (13), Nd (14)) having indolyl ligands in μ-η5:η1:η1 hapticities. The pathway for the transformation of the amino group to the imino group is proposed on the basis of the experimental results. The new complexes displayed excellent activity in the intramolecular hydroamination of aminoalkenes.
2,5-Bis{ N -(2,6-diisopropylphenyl)iminomethyl}pyrrolyl complexes of the heavy alkaline earth metals: Synthesis, structures, and hydroamination catalysis
Jenter, Jelena,Koeppe, Ralf,Roesky, Peter W.
experimental part, p. 1404 - 1413 (2011/04/25)
The heteroleptic iodo complexes [(DIP2pyr)MI(THF)n] (M = Ca, Sr (n = 3); Ba (n = 4); (DIP2pyr)- = 2,5-bis{N-(2,6-diisopropylphenyl)iminomethyl}pyrrolyl) were synthesized by reaction of [(DIP2pyr)K] with anhydrous alkaline earth metal diiodides. All complexes are monomeric in the solid state. A κ3-coordination mode of the (DIP2pyr)- ligand was observed for the strontium and the barium compounds, while the analogous calcium derivative is κ2-coordinated in the solid state. However, VT-1H NMR studies of [(DIP2pyr)CaI(THF) 3] indicate a symmetrically coordinated (DIP2pyr) - ligand in solution. Computational studies confirm the different coordination modes in solution and in the solid state. The preferred κ2-coordination mode observed in the solid state might be a result of temperature or/and crystal-packing effects. Furthermore, the calcium and strontium amido complexes [(DIP2pyr)M{N(SiMe3) 2}(THF)2] (M = Ca, Sr) were prepared by reaction of [(DIP2pyr)MI(THF)n] (M = Ca, Sr (n = 3)) with [K{N(SiMe3)2}]. Both compounds were investigated for the intramolecular hydroamination of aminoalkenes. Both catalysts showed a good activity, and the best results were obtained for the calcium complex [(DIP 2pyr)Ca{N(SiMe3)2}(THF)2].