A General Acid‐Mediated Hydroaminomethylation of Unactivated Alkenes and Alkynes. Issue 41 (4th September 2019)

• Record Type: Journal Article
• Authors: Kaiser, Daniel; Tona, Veronica; Gonçalves, Carlos R.; Shaaban, Saad; Oppedisano, Alberto; Maulide, Nuno
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 41(2019)
• Page Start: 14639
• Page End: 14643
• Publication Date: 2019-09-04
• Subjects: amines -- hydroaminoalkylation -- hydroaminomethylation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201906910
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: In comparison to the extensively studied metal‐catalyzed hydroamination reaction, hydroaminomethylation has received significantly less attention despite its considerable potential to streamline amine synthesis. State‐of‐the‐art protocols for hydroaminomethylation of alkenes rely largely on transition‐metal catalysis, enabling this transformation only under highly designed and controlled conditions. Here we report a broadly applicable, acid‐mediated approach to the hydroaminomethylation of unactivated alkenes and alkynes. This methodology employs cheap, readily available, and bench‐stable reactants and affords the desired amines with excellent functional group tolerance and impeccable regioselectivity. The broad scope of this transformation, as well as mechanistic investigations and in situ domino functionalization reactions are reported. Abstract : Amines on the cheap : In comparison to the hydroamination reaction, hydroaminomethylation, the addition of a hydrogen and a (methyleneamino) unit across an olefin, has received significantly less attention. A broadly applicable, acid‐mediated strategy for the hydroaminomethylation of unactivated alkenes and alkynes has been developed using cheap and bench‐stable reactants.