Intramolecular Hydroalkoxylation/Reduction and Hydroamination/Reduction of Unactivated Alkynes Using a Silane–Iodine Catalytic System

A transition-metal-free silane–iodine catalytic system comprising I 2 and Et 3 SiH promotes intramolecular hydroalkoxylation/reduction and hydroamination/reduction of unactivated alkynes. This system allows the reaction to proceed at room temperature affording 2,4- and 2,5-disubstituted pyrrolidines as well as a 2,3-disubstituted tetrahydrofuran with high diastereoselectivity.