Aryne Precursors for Selective Generation of 3-Haloarynes: Preparation and Application to Synthetic Reactions.

The synthesis and reaction of new 3-haloaryne precursors 2a-2h were studied. The ortho-(trimethylsilyl)aryl triflate precursors 2a-2h were prepared by a simple procedure involving O-trimethylsilylation and migration of a trimethylsilyl group followed by triflation. The remarkable feature of new precursors is the selective generation of 3-haloarynes by suppressing the competitive thia-Fries rearrangement, which is the problem in the reaction using the well-known 3-haloaryne precursors. The advantage of new precursor 2a over a typical precursor 1 was confirmed by the direct comparisons in several reactions. The application of precursors 2a-2h to the syntheses of heterocycles was also reported.