Picolinamides and Iodoalkynes Enable Palladium-Catalyzed syn-Aminoalkynylation of Di- and Trisubstituted Alkenes to Give Pyrrolidines

Palladium-catalyzed aminoalkynylation of electronically unbiased olefins with iodoalkynes is reported. The picolinamide auxiliary enables for the first time the syn-selective aminoalkynylation of mono-, di- and trisubstituted alkenes to afford the corresponding pyrrolidines in up to 97 % yield and as single diastereomers. Furthermore, through a C-H activation approach, the picolinamide allows the rapid synthesis of functionalized olefins, which are suitable cyclization precursors. Facile and orthogonal deprotection of the amides and (SiPr3)-Pr-i-acetylenes in the products, and a subsequent Pictet-Spengler reaction is demonstrated.

Automated summary

In this study, the palladium-catalyzed aminoalkynylation of electronically unbiased olefins with iodoalkynes was reported. Using the picolinamide auxiliary, the syn-selective aminoalkynylation of mono-, di-, and trisubstituted alkenes was achieved, leading to the formation of corresponding pyrrolidines in high yield and single diastereomers. The picolinamide also allowed for the rapid synthesis of functionalized olefins and subsequent Pictet-Spengler reaction.