Ni-Catalyzed Suzuki-Miyaura Cross-Coupling of α-Oxo-vinylsulfones To Prepare C-Aryl Glycals and Acyclic Vinyl Ethers

We demonstrate that readily available and bench-stable alpha-oxo-vinylsulfones are competent electrophiles in Ni-catalyzed Suzuki-Miyaura cross-coupling reactions. The C-sulfone bond in the alpha-oxo-vinylsulfone motif is cleaved chemoselectively in these reactions, furnishing C-aryl glycals or acyclic vinyl ethers in high yields. These reactions proceed under mild conditions and tolerate a remarkable scope of heterocycles and functional groups. Preliminary mechanistic studies revealed the importance of an alpha-heteroatom in facilitating these transformations.