One-Pot, Telescoped Aryl Nitrile Synthesis from Benzylic Silyl Ethers.

A one-pot, telescoped transformation of silyl ethers into cyanides that proceeds via silyl-ether oxidation mediated by nitroxyl-radical catalyst 1 and [bis(trifluoroacetoxy)iodo]benzene followed by an imine formation-oxidation sequence using iodine and aqueous ammonia is reported. This transformation is effective for the site-selective transformation of benzylic and allylic silyl ethers in the presence of other silyl ethers. Using an O-protected oxime and a catalytic amount of triflic acid instead of iodine/aqueous ammonia is also effective for cyanation.