Stereoselective Synthesis of Tertiary Allylic Amines by Titanium‐Catalyzed Hydroaminoalkylation of Alkynes with Tertiary Amines. Issue 10 (25th January 2022)

• Record Type: Journal Article
• Authors: Kaper, Tobias; Geik, Dennis; Fornfeist, Felix; Schmidtmann, Marc; Doye, Sven
• Is Part Of: Chemistry. Volume 28:Issue 10(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-25
• Subjects: alkynes -- amines -- C−H activation -- hydroaminoalkylation -- titanium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202103931
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Intermolecular hydroaminoalkylation reactions of symmetrical and unsymmetrical alkynes with tertiary amines take place in the presence of catalytic amounts of TiBn4, Ph3 C[B(C6 F5 )4 ], and a sterically demanding aminopyridinato ligand precursor. The resulting products, synthetically and pharmaceutically useful tertiary β, γ‐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. Abstract : Unsymmetrical and symmetrical alkynes undergo hydroaminoalkylation with tertiary amines in the presence of a cationic titanium catalyst system, which is generated in situ. The products obtained are synthetically and pharmaceutically very interesting tertiary allylamines, which are formed in very good yields (up to 99 %) and with excellent stereoselectivity. A major highlight of the work is the successful conversion of trimethylamine into N, N ‐dimethyl‐ E ‐allylamines.