Unprecedented Selectivity via Electronic Substrate Recognition in the 1,4‐Addition to Cyclic Olefins Using a Chiral Disulfoxide Rhodium Catalyst

From zero to hero? Sulfoxides are generally not considered useful ligand entities in asymmetric metal catalysis. However, a chiral disulfoxide as a chelating ligand in the rhodium-catalyzed 1,4-addition of aryl boronic acids to cyclic, alpha,beta-unsaturated ketones and esters gives impressive catalytic results, thus opening the door to future applications of this new chiral ligand class.