Iron-Catalyzed Ring-Opening Azidation and Allylation of <i>O</i>‑Heterocycles

We have established the first catalytic C–C and C–N bond formation reactions of <i>O</i>-heterocycles (e.g., tetrahydrofuran, phthalane, and lactone derivatives) using iron trichloride as a catalyst in the presence of TMSN<sub>3</sub> or allylsilanes accompanied by the ring opening of <i>O</i>-heterocycles. The reactions smoothly proceeded at room temperature to give the corresponding primary saturated alcohols from the 2-substituted tetrahydrofurans, <i>ortho</i>-substituted benzyl alcohols from phthalanes, and saturated carboxylic acids from lactones in high yields.