39074-69-6Relevant academic research and scientific papers
An Aminopyridinato Titanium Catalyst for the Intramolecular Hydroaminoalkylation of Secondary Aminoalkenes
D?rfler, Jaika,Bytyqi, Besnik,Hüller, Sascha,Mann, Nicola M.,Brahms, Christian,Schmidtmann, Marc,Doye, Sven
supporting information, p. 2265 - 2276 (2015/07/27)
The easily accessible 2-(methylamino)pyridinato titanium complex initially synthesized by Kempe is used as catalyst for efficient intramolecular hydroaminoalkylation reactions of secondary aminoalkenes. The corresponding reactions of N-aryl-substituted 1-aminohept-6-enes and 1-aminohex-5-enes directly give access to 2-methylcyclohexyl- or 2-methylcyclopentylamines in good yields. In addition, intramolecular hydroaminoalkylations of an N-alkyl-substituted secondary aminoalkene and a geminally β-disubstituted substrate are described for the first time. While all products are formed as mixtures of two diastereoisomers, better trans/cis ratios are observed during the formation of 2-methylcylopentylamines.
Direct, catalytic hydroaminoalkylation of unactivated olefins with N-alkyl arylamines
Herzon, Seth B.,Hartwig, John F.
, p. 6690 - 6691 (2008/02/06)
A tantalum-catalyzed addition of N-alkyl arylamine ∞-C-H bonds across olefins is reported. These reactions occur with mono- and 2,2-disubstituted olefins to form the branched insertion products in high yield and regioselectivity. The reactions encompass additions of the ∞-C-H bonds of cyclic and acyclic amines, as well as intramolecular additions. NMR studies indicate that the starting homoleptic, Ta(NMe2)5 precatalyst converts to bis- and tris(N-methylanilide) complexes (among others) in solution. Deuterium-labeling studies suggest that reversible ortho-metalation of the arene substituent occurs under the reaction conditions. However, several experiments imply that this ortho-metalation does not lie on the reaction pathway. Instead, these complexes are proposed to eliminate amine to form N-aryl imine complexes, which insert olefins into the Ta-C bond and undergo protonolysis to regenerate the active catalyst and eliminate the addition product. Copyright
