The regioselectivec onversiono fa lkyl-substituted alkenes into linear hydroaminoalkylation productsr epresentsastrongly desirable synthetic transformation. In Scheme1.Hydroaminoalkylation of allylbenzene(2)w ith N-methylaniline (1).

Intermolecular hydroaminoalkylation reactions of propadiene with selected secondary amines take place in the presence of a2 ,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 at itanaaziridine.

A new two‐step procedure that includes an initial regioselective intermolecular hydroaminoalkylation of ortho‐chlorostyrenes with N‐methylanilines and a subsequent intramolecular Buchwald–Hartwig amination gives direct access to 1,2,3,4‐tetrahydroquinolines. The hydroaminoalkylation reaction of the ortho‐chlorostyrenes is catalyzed by a 2,6‐bis(phenylamino)pyridinato titanium complex which delivers the linear regioisomers with high selectivities. In addition, the formation of unexpected dihydroaminoalkylation products from styrenes and N‐methylanilines is reported.

New two‐step procedures that include an initial regioselective intermolecular hydroaminoalkylation of 2‐allyl‐, 2‐allyldimethylsilyl‐, or 2‐dimethyl(vinyl)silyl‐substituted 3‐bromothiophenes or 3‐bromobenzothiophenes with secondary amines and a subsequent intramolecular Buchwald‐Hartwig amination give direct access to structurally novel bicyclic heterocycles including tetrahydrothienopyridines, tetrahydrothienoazasilines, tetrahydrobenzothienoazasilines, and tetrahydrobenzothienoazasilepines. The hydroaminoalkylation reaction is catalyzed by a mono(aminopyridinato) titanium complex which delivers the branched hydroaminoalkylation products or in the case of vinylsilyl‐substituted substrates, the use of a bis(aminopyridinato) titanium complex gives access to the linear regioisomers. While in the latter case, the hydroaminoalkylation products need to be purified prior to the palladium‐catalyzed amination step, all other two‐step sequences can be run as a one‐pot procedure.

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