Oxidatively Triggered Carbon–Carbon Bond Formation in Ene-amide Complexes
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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 {η3-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.
创建时间：
2016-04-26
