87 research outputs found

    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 CrCl<sub>2</sub>, Cl<sub>2</sub>Fe­(PMe<sub>3</sub>)<sub>2</sub>, and Cl<sub>2</sub>Copy<sub>4</sub> with 2 equiv of {(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)­(1-<sup>c</sup>Hexenyl)­N}Li afforded pseudosquare planar {η<sup>3</sup>-C,C,N-(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)­(1-<sup>c</sup>Hexenyl)­N}<sub>2</sub>Cr (<b>1</b>-Cr, 78%), trigonal {(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)­(1-<sup>c</sup>Hexenyl)­N}<sub>2</sub>Fe­(PMe<sub>3</sub>) (<b>2</b>-Fe, 80%), and tetrahedral {(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)­(1-<sup>c</sup>Hexenyl)­N}<sub>2</sub>Co­(py)<sub>2</sub> (<b>3</b>-Co, 91%) in very good yields. The addition of CrCl<sub>3</sub> to <b>1</b>-Cr, and FeCl<sub>3</sub> to <b>2</b>-Fe, afforded oxidatively triggered C–C bond formation as <i>rac</i>-2,2′-di­(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>N)<sub>2</sub>dicyclohexane (<b>EA</b><sub>2</sub>) 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., <b>2</b>-Fe, FeCl<sub>2</sub>) were shown to catalyze C-arylation of {(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)­(1-<sup>c</sup>Hexenyl)­N}Li with PhBr, but the reaction was variable. Structural characterizations of <b>1</b>-Cr, <b>2</b>-Fe, and <b>3</b>-Co are reported

    Oxidatively Triggered Carbon–Carbon Bond Formation in Ene-amide Complexes

    No full text
    Ene-amides have been explored as ligands and substrates for oxidative coupling. Treatment of CrCl<sub>2</sub>, Cl<sub>2</sub>Fe­(PMe<sub>3</sub>)<sub>2</sub>, and Cl<sub>2</sub>Copy<sub>4</sub> with 2 equiv of {(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)­(1-<sup>c</sup>Hexenyl)­N}Li afforded pseudosquare planar {η<sup>3</sup>-C,C,N-(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)­(1-<sup>c</sup>Hexenyl)­N}<sub>2</sub>Cr (<b>1</b>-Cr, 78%), trigonal {(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)­(1-<sup>c</sup>Hexenyl)­N}<sub>2</sub>Fe­(PMe<sub>3</sub>) (<b>2</b>-Fe, 80%), and tetrahedral {(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)­(1-<sup>c</sup>Hexenyl)­N}<sub>2</sub>Co­(py)<sub>2</sub> (<b>3</b>-Co, 91%) in very good yields. The addition of CrCl<sub>3</sub> to <b>1</b>-Cr, and FeCl<sub>3</sub> to <b>2</b>-Fe, afforded oxidatively triggered C–C bond formation as <i>rac</i>-2,2′-di­(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>N)<sub>2</sub>dicyclohexane (<b>EA</b><sub>2</sub>) 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., <b>2</b>-Fe, FeCl<sub>2</sub>) were shown to catalyze C-arylation of {(2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)­(1-<sup>c</sup>Hexenyl)­N}Li with PhBr, but the reaction was variable. Structural characterizations of <b>1</b>-Cr, <b>2</b>-Fe, and <b>3</b>-Co are reported
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