Synthesis of β-Acetoxy Alcohols by PhI(OAc)2-Mediated Metal-Free Diastereoselective β-Acetoxylation of Alcohols.

β-Acetoxy alcohols can be synthesized in good yields with excellent diastereoselectivity from tertiary alcohols through PhI(OAc)2-mediated metal-free β-acetoxylation. Mechanistic studies showed that the β-acetoxylation process might undergo dehydration and sequential highly regioselective and diastereoseletive dioxygenation. Gram scale and diverse useful scaffolds could be prepared via this β-acetoxylation process.