Transition metal‐catalyzed enantioselective C−H activation of prochiral sulfoximines for non‐annulated products remains a formidable challenge. We herein report iridium‐catalyzed enantioselective C−H borylation of N‐silyl diaryl sulfoximines using a well‐designed chiral bidentate boryl ligand with a bulky side arm. This method is capable of accommodating a broad range of substrates under mild reaction conditions, affording a vast array of chiral sulfoximines with high enantioselectivities. We also demonstrated the synthetic utility on a preparative‐scale C−H borylation for diverse downstream transformations, including the synthesis of chiral version of bioactive molecules. Computational studies showed that the bulky side arm of the ligand confers high regio‐ and enantioselectivity through steric effect.

P-stereogenic phosphorus compounds are a ubiquitous and critically important class of chiral ligands in asymmetric catalysis. Methods for catalytic asymmetric synthesis via a step- and atom-economic way are still very limited. We herein disclose a protocol of phosphinate-directed iridium-catalyzed enantioselective ortho-H borylation to construct P-stereogenic phosphorus compounds. A number of functional groups could be well tolerated to afford optically active diarylphosphinates with good to excellent enantioselectivities (up to 92% ee). We also demonstrate the synthetic utilities of the obtained borylated products, including the synthesis of precursors for chiral phosphine ligands.