10.1021/om050768y.s004 Denis A. Kissounko Denis A. Kissounko Ilia A. Guzei Ilia A. Guzei Samuel H. Gellman Samuel H. Gellman Shannon S. Stahl Shannon S. Stahl Titanium(IV)-Mediated Conversion of Carboxamides to Amidines and Implications for Catalytic Transamidation American Chemical Society 2005 Conversion Catalytic Transamidation amidine amide dimethylacetamide transamidation PhCH complex amide phenylacetamide forms contrast amidate adduct Carboxamide fragment carboxamide MeC 6 H 4 C 5 imidotitanium MeOC 6 H 4 Implication TiCl Amidine t Bu exogenous amine Cp C 5 H 11 2005-10-24 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Titanium_IV_Mediated_Conversion_of_Carboxamides_to_Amidines_and_Implications_for_Catalytic_Transamidation/3261649 Cp*-ligated imidotitanium(IV) complexes, Cp*TiCl(NR)(py)Cl (R = <i>t</i>Bu (<b>5a</b>), PhCH<sub>2</sub> (<b>5b</b>), <i>n</i>-C<sub>5</sub>H<sub>11</sub> (<b>5c</b>), <i>p</i>-MeC<sub>6</sub>H<sub>4</sub> (<b>5d</b>), <i>p</i>-MeOC<sub>6</sub>H<sub>4</sub> (<b>5e</b>)), react with tertiary and secondary carboxamides to yield amidines, a result that is in contrast with previously reported titanium-catalyzed transamidation reactions. The tertiary amide dimethylacetamide reacts directly with the imidotitanium(IV) fragment, whereas the secondary amide phenylacetamide forms an amidate adduct, {(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)TiCl[OC(Me)NPh]<sub>2</sub>} (<b>10</b>), which undergoes subsequent reaction with exogenous amine.