Structural Tuning of Inefficient <i>C</i> ₁ -Symmetric Iodoarene for Efficient Enantioselective Oxidative Organocatalysis

A new iodoarene catalyst with <i>C</i> ₁ symmetry was developed for enantioselective oxidative transformations. Notably, in the α-tosyloxylation of ketones, the catalyst delivered up to 85% yield and 75% <i>ee</i>. Comparative studies showed superior selectivity over analogs with <i>C</i> ₂ symmetry, which yielded racemic products. Density function theory (DFT) studies revealed a key stereodetermining complex in the reaction mechanism, supporting the origin of the enantioselectivity. The broad substrate scope demonstrates the versatility of the catalyst. These results emphasize the value of the <i>C</i> ₁-symmetric design for chiral hypervalent iodine catalysis.