A series of pyridonate and amidate supported titanium alkoxides have been isolated. These complexes can be readily prepared in high yield, under mild reaction conditions in only two steps from commercially available (Ti(NMe(2))(4)). We have furnished one of the rare examples of discrete catalysts for random copolymer synthesis.

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Yttrium (amidate) precatalysts are highly active for the mild amidation of aldehydes with amines. Reactions occur at room temperature within 5 min in up to 98% isolated yield. These rare-earth systems are effective for this transformation in the absence of supplementary heat, light, base, or oxidants. The reaction proceeds with functionalized amines and/or aldehydes. A comparison of various amidate precatalysts in combination with reaction monitoring suggests that the targeted amide products formed during the reaction promote the formation of alternative catalytically active amidate species in situ.

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