Intermolecular Hydroaminoalkylation of Propadiene

Intermolecular hydroaminoalkylation reactions of propadiene with selected secondary amines take place in the presence of a 2,6‐bis(phenylamino)pyridinato titanium catalyst. The corresponding products, synthetically useful allylamines, are formed in convincing yields and with high selectivities. In addition, propadiene easily inserts into the titanium‐carbon bond of a titanaaziridine. Propadiene undergoes regioselective hydroaminoalkylation reactions with N‐aryl‐ and N‐alkyl‐substituted benzylamines in the presence of an aminopyridinato titanium catalyst. The corresponding products, synthetically useful allylamines, are formed in very good yields (up to 97 %) and with regioselectivities as high as 99:1.