Aryl Silyl Ethers Enable Preferential Ar-O bond Cleavage in Reductive Generation of Aryllithium Species

Two-electron transfer to haloarenes constitutes one of the most reliable synthetic methodologies for the generation of aryllithiums. In addition to the conventional halides, readily available aryl ethers can function as potent substrates. However, it is known that the reductive cleavage of alkoxides is plagued by insufficient selectivity concerning the cleaving bond adjacent to the ether oxygen, resulting in decreased reliability of these alkoxyarene substrates. In the present study, we discovered that naphthalenes bearing readily installable tert-butyldimethylsilyl ethers undergo two-electron reduction with lithium metal, resulting in lithiation at the position of the original siloxy group. DFT calculations elucidated the rationale for the change in selectivity upon incorporation of the siloxy group. Our results underscore the practical utility of a siloxy group as a leaving group for reductive transformations involving electron transfer.