Structural Tuning of Inefficient C 1‑Symmetric Iodoarene for Efficient Enantioselective Oxidative Organocatalysis.

A new iodoarene catalyst with C 1 symmetry was developed for enantioselective oxidative transformations. Notably, in the α-tosyloxylation of ketones, the catalyst delivered up to 85% yield and 75% ee. Comparative studies showed superior selectivity over analogs with C 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 C 1-symmetric design for chiral hypervalent iodine catalysis.