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.