700378-28-5Relevant articles and documents
Cyclopentadienyl-based Mg complexes in the intramolecular hydroamination of aminoalkenes: Mechanistic evidence for cationic: Versus neutral magnesium derivatives
Gallegos, Carlos,Camacho, Ruth,Valiente, Mercedes,Cuenca, Tomás,Cano, Jesús
, p. 5134 - 5143 (2016/07/07)
Neutral and cationic magnesium complexes stabilized by coordination of a cyclopentadienyl ligand with two different neutral hemilabile donor groups [Mg{η5-C5H3-1,3-(CH2CH2NiPr2)(SiMe2NPh2)}X(thf)] (X = Bz (2); N(SiMe3)2 (3)) and [Mg{η5-C5H3-1,3-(CH2CH2NiPr2)(SiMe2NPh2)}][BPh4] (4) have been prepared and characterized. The 1H-13C HMBC and HSQC spectra of compounds 2 and 3 demonstrate the formation of 1,3-substituted cyclopentadienyl compounds and DOSY and 1H-NMR experiments support the coordination-decoordination in solution of a THF molecule in complex 2. No Schlenk-type ligand redistributions were observed in the chemical behaviour of these magnesium complexes. Compounds 2-4 are active catalysts in the hydroamination of aminoalkenes; stoichiometric reactions and kinetic measurements have been performed to gain an insight into their reaction mechanisms. A key contribution here is the catalytic reactivity of a cationic magnesium compound.
New highly active heteroscorpionate-containing lutetium catalysts for the hydroamination of aminoalkenes: Isolation and structural characterization of a dipyrrolidinide-lutetium complex
Otero, Antonio,Lara-Sanchez, Agustin,Najera, Carmen,Fernandez-Baeza, Juan,Marquez-Segovia, Isabel,Castro-Osma, Jose Antonio,Martinez, Javier,Sanchez-Barba, Luis F.,Rodriguez, Ana M.
scheme or table, p. 2244 - 2255 (2012/06/04)
The reactions of the hybrid scorpionate/cyclopentadiene compounds, as a mixture of regioisomers-1-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl]- 1,3-cyclopentadiene and 2-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl]- 1,3-cyclopentadiene (
Intramolecular hydroamination of aminoalkenes catalyzed by a cationic zirconium complex
Wang, Xinke,Chen, Zhou,Sun, Xiu-Li,Tang, Yong,Xie, Zuowei
supporting information; experimental part, p. 4758 - 4761 (2011/10/30)
A new cationic [N-O-S]zirconium complex (cat.) was developed to be an excellent catalyst for the intramolecular hydroamination of aminoalkenes with a large substrate scope from terminal alkenes to internal alkenes, and primary amines to secondary amines. The catalyst system can also tolerate various functional groups and perform sequential hydroamination of primary aminodienes.
Highly efficient, base-catalysed, intramolecular hydroamination of non-activated olefins
Quinet, Coralie,Jourdain, Pierre,Hermans, Christophe,Ates, Ali,Lucas, Isabelle,Markó, István E.
, p. 1077 - 1087 (2008/09/17)
The intramolecular hydroamination of a large variety of non-activated alkenes can be efficiently catalysed by small amounts of lithium bases, providing smoothly and in high yields the corresponding five- and six-membered ring heterocycles. Fused and bridged bicyclic amines, of varying ring sizes, can be readily prepared either by a sequential hydroamination process or by a tandem, double addition reaction.
Base-catalysed asymmetric hydroamination/cyclisation of aminoalkenes utilising a dimeric chiral diamidobinaphthyl dilithium salt
Martinez, Patricia Horrillo,Hultzsch, Kai C.,Hampel, Frank
, p. 2221 - 2223 (2007/10/03)
A dimeric proline derived diamidobinaphthyl dilithium salt represents the first example of a chiral main group metal based catalyst for asymmetric hydroamination/cyclisation reactions of aminoalkenes. The Royal Society of Chemistry 2006.
Non-metallocene rare earth metal catalysts for the diastereoselective and enantioselective hydroamination of aminoalkenes
Hultzsch, Kai C.,Gribkov, Denis V.,Hampel, Frank
, p. 4441 - 4452 (2007/10/03)
In this short review we summarize our work on new cyclopentadienyl-free rare earth metal catalysts for the diastereoselective and enantioselective hydroamination of aminoalkenes. Non-metallocene rare earth metal catalysts based on diamidoamine, biphenolate and binaphtholate ligands are readily available through alkane and amine elimination procedures. Diamidoamine yttrium complexes are efficient catalysts for the highly diastereoselective cyclization of 1-methyl-pent-4-enylamine to yield trans-2,5-dimethyl-pyrroldine with trans to cis ratios of up to 23:1. The X-ray crystal structural analysis of [((2,6-Et2C6H3NCH2CH 2)2NMe)Y{N(SiMe3)2}] is reported in which yttrium is coordinated in a highly distorted tetrahedral fashion. 3,3′-Di-tert-butyl substituted biphenolate complexes tend to form phenolate-bridged hetero- and homochiral dimers. The low steric demand of the tert-butyl substituents resulted also in low enantioselectivities in hydroamination/cyclization reactions. Binaphtholate complexes with sterically more demanding tris(aryl)silyl substituents were more efficient catalysts; giving enantioselectivities of up to 83% ee. These catalysts could also be applied in kinetic resolution of chiral aminoalkenes giving krel values as high as 16. Catalyst activities strongly depend on the reactivity of the leaving group which is protolytically exchanged for the substrate during the initiation step. Complexes with bis(dimethylsilyl)amido ligand initiate rather sluggishly because of the low basicity of this amido ligand and appreciable catalytic activity is only observed at elevated temperatures. Aryl and Alkyl complexes showed significant better rates comparable in magnitude to lanthanocene catalysts.
