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.