Enantioselective Assembly of Si‐Stereogenic Sila‐[1,4]oxazines via Sequential Si─O/Si─C Dehydrocoupling

Silacycles have shown great promise in medicinal chemistry, agrochemistry, and materials science. In this study, we report an efficient iridium‐catalyzed enantioselective dehydrogenative coupling of pyrrolo‐phenol derivatives with dihydrosilanes, which leads to the synthesis of Si‐stereogenic sila‐[1,4]oxazines with excellent enantioselectivity. This method successfully integrates silicon into the bioactive [1,4]oxazine framework, broadening the application scope of silicon‐containing heterocycles. Mechanistic studies indicate a two‐step sequence: an enantioselective Ir‐catalyzed Si─O dehydrocoupling, followed by an intramolecular Si─C coupling.