N-(Trimethylsilyl)amines direct ring-openingcarbonylation of a variety of cyclicethers such as oxiranes (1–3), oxetane (4), tetrahydrofuran (5), and 1,3-dioxolane (6) in the presence of a catalytic amount of Co2(CO)8 under carbon monoxide pressure to give siloxy amides.
Co2(CO)8-catalyzed ring-opening carbonylation of oxiranes and oxetane smoothly proceeds with high regioselectivity under 1 atm of carbon monoxide at room temperature to give the corresponding β- and γ-siloxy amides in high yields, respectively. [(R3Si)2NR1R2]+[Co(CO)4]− is thought to be an active catalyst species and directs the high regioselectivity of the carbonylation.