Anti-Markovnikov intermolecular hydroamination: a bis(amidate) titanium precatalyst for the preparation of reactive aldimines.

[reaction: see text] A bulky bis(N-2',6'-diisopropylphenyl(phenyl)-amidate)titanium-bis(diethylamido) complex was identified as a highly active and regioselective precatalyst for the anti-Markovnikov hydroamination of a wide range of terminal alkyl alkynes with alkylamines. This titanium complex was fully characterized, including its X-ray crystal structure. The reactive aldimine products generated have been further elaborated using one-pot procedures to give substituted amines, aldehydes, and the isoquinoline framework.