We report a diversification strategy for phosphines that enables the direct substituent exchange of tertiary phosphines. Alkylated phosphonium salts, prepared by standard alkylation of phosphines, are selectively dearylated in a...

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 SiiPr3‐acetylenes in the products, and a subsequent Pictet–Spengler reaction is demonstrated.

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-, diand trisubstituted alkenes to afford the corresponding pyrrolidines in up to 97 % yield and as single diastereomers. Furthermore, through a CÀ 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 Si i Pr 3 -acetylenes in the products, and a subsequent Pictet-Spengler reaction is demonstrated.