American Chemical Society
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TiIV-Mediated Reactions between Primary Amines and Secondary Carboxamides:  Amidine Formation Versus Transamidation

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posted on 2007-02-14, 00:00 authored by Denis A. Kissounko, Justin M. Hoerter, Ilia A. Guzei, Qiang Cui, Samuel H. Gellman, Shannon S. Stahl
Titanium(IV)-mediated reactions between primary amines and secondary carboxamides exhibit different outcomes, amidine formation versus transamidation, depending on the identity of the TiIV complex used and the reaction conditions employed. The present study probes the origin of this divergent behavior. We find that stoichiometric TiIV, either Cp*TiIV complexes or Ti(NMe2)4, promotes formation of amidine and oxotitanium products. Under catalytic conditions, however, the outcome depends on the identity of the TiIV complex. Competitive amidine formation and transamidation are observed with Cp*TiIV complexes, generally favoring amidine formation. In contrast, the use of catalytic Ti(NMe2)4 (≤20 mol %) results in highly selective transamidation. The ability of TiIV to avoid irreversible formation of oxotitanium products under the latter conditions has important implications for the use of TiIV in catalytic reactions.