Smiles-Rearrangement-Based One-Pot Synthesis of Diarylacetylenes from Benzylic Sulfones and Methyl Benzoates Mediated by LiN(SiMe3)2/KN(SiMe3)2

The one-pot synthesis of diphenylacetylene by the reaction of methyl benzoate with 1-(benzylsulfonyl)-3,5-di(trifluoromethyl)benzene was developed. The combination of LiN(SiMe3)2 and KN(SiMe3)2 is key to promoting the reaction. Simply combining methyl benzoate, 1-(benzylsulfonyl)-3,5-di(trifluoromethyl)benzene, LiN(SiMe3)2, and KN(SiMe3)2 can produce a variety of diaryl acetylenes (28 examples, 18–70% yields).