75251-09-1Relevant academic research and scientific papers
Oxidatively Triggered Carbon-Carbon Bond Formation in Ene-amide Complexes
Jacobs, Brian P.,Wolczanski, Peter T.,Lobkovsky, Emil B.
supporting information, p. 4223 - 4232 (2016/05/24)
Ene-amides have been explored as ligands and substrates for oxidative coupling. Treatment of CrCl2, Cl2Fe(PMe3)2, and Cl2Copy4 with 2 equiv of {(2,6-iPr2C6H3)(1-cHexenyl)N}Li afforded pseudosquare planar {3-C,C,N-(2,6-iPr2C6H3)(1-cHexenyl)N}2Cr (1-Cr, 78%), trigonal {(2,6-iPr2C6H3)(1-cHexenyl)N}2Fe(PMe3) (2-Fe, 80%), and tetrahedral {(2,6-iPr2C6H3)(1-cHexenyl)N}2Co(py)2 (3-Co, 91%) in very good yields. The addition of CrCl3 to 1-Cr, and FeCl3 to 2-Fe, afforded oxidatively triggered C-C bond formation as rac-2,2′-di(2,6-iPr2C6H3N - )2dicyclohexane (EA2) was produced in modest yields. Various lithium ene-amides were similarly coupled, and the mechanism was assessed via stoichiometric reactions. Some ferrous compounds (e.g., 2-Fe, FeCl2) were shown to catalyze C-arylation of {(2,6-iPr2C6H3)(1-cHexenyl)N}Li with PhBr, but the reaction was variable. Structural characterizations of 1-Cr, 2-Fe, and 3-Co are reported.
Azomethines, 1-Azaallyl Anions, and Metastable Secondary Enamines
Knorr, Rudolf,Weiss, Alfons,Loew, Peter,Raepple, Edith
, p. 2462 - 2489 (2007/10/02)
E/Z equilibrium constants of the ketone anils 6a-s do not depend significantly on the inductive substituent effect. 1H NMR chemical shifts used for configurational classification are also effective for assignments in comparable, isomerically almost pure azomethines 6aa-pp and may be explained by the anisotropic shift model.The 1-azaallyl anions 7 prepared by deprotonation are characterized by 1H NMR spectroscopy.Kinetic and thermodynamic control of this metallation reaction result in different preferential configurations of such anions, the methanolysis of which yields metastable sec. enamines 8 by regio- and stereospecific N-protonation.It is possible to estimate further substituent parameters λd from E/Z equilibria.
