Regiodivergent Synthesis of Oxadiazocines via Dirhodium-Cata- lyzed Reactivity of Oxazolidines and ?-Imino Carbenes

Using electron-rich or electron-poor N-substituted oxazolidines as substrates, selective formation of either ammonium or oxonium ylides is possible in the presence of ?-imino carbenes. As such, treatment of 5-membered oxazolidine precursors with N-sulfonyl-1,2,3-triazoles under dirhodium catalysis (2 mol%) affords the regiodivergent synthesis of either 8-membered 1,3,6-or 1,4,6-oxadiazocines upon the initial N or O reactivity with the carbene.

Automated summary

By using electron-rich or electron-poor N-substituted oxazolidines as substrates, it is possible to selectively form either ammonium or oxonium ylides with the presence of ?-imino carbenes. Under dirhodium catalysis (2 mol%), treatment of 5-membered oxazolidine precursors with N-sulfonyl-1,2,3-triazoles allows for the regiodivergent synthesis of either 8-membered 1,3,6- or 1,4,6-oxadiazocines based on the initial N or O reactivity with the carbene.