Stereoselective Synthesis of Tertiary Allylic Amines by Titanium-Catalyzed Hydroaminoalkylation of Alkynes with Tertiary Amines

Intermolecular hydroaminoalkylation reactions of symmetrical and unsymmetrical alkynes with tertiary amines take place in the presence of catalytic amounts of TiBn4, Ph3C[B(C6F5)(4)], and a sterically demanding aminopyridinato ligand precursor. The resulting products, synthetically and pharmaceutically useful tertiary beta,gamma-disubstituted allylic amines, are formed in convincing yields and with excellent stereoselectivity. Particularly promising for future applications is the fact that even the industrial side product trimethylamine can be used as a substrate.

Automated summary

Intermolecular hydroaminoalkylation reactions of symmetrical and unsymmetrical alkynes with tertiary amines were achieved with catalytic amounts of TiBn4, Ph3C[B(C6F5)(4)], and a sterically demanding aminopyridinato ligand precursor. The resulting products, synthetically and pharmaceutically useful tertiary beta,gamma-disubstituted allylic amines, were obtained in high yields and excellent stereoselectivity. The fact that even the industrial side product trimethylamine can be used as a substrate is particularly promising for future applications.