NIS-Promoted Selective Amino-Diazidation and Amino- Iodoazidation of O-Homoallyl Benzimidates: Synthesis of Vicinal Diazido 1,3-Oxazines and Vicinal Iodoazido 1,3-Oxazines

Amines, especially those with multi-nitrogen moieties, are widespread in natural products and biologically active compounds. Thus, the development of direct and efficient methods to introduce multiple nitrogen-containing fragments into compounds in one step is highly desirable yet challenging. Herein, we report an NIS-promoted selective amino-diazidation and amino-iodoazidation of O-homoallyl benzimidates with NaN3. By using this protocol, a variety of vicinal diazido-substituted 1,3oxazines and vicinal iodoazido-substituted 1,3-oxazines were directly synthesized in a controllable manner. Preliminary mechanistic investigations revealed that the reaction operates through a NIS-promoted four-step cascade process. The developed method has the merits of metal-free, excellent functional group compatibility, simple operation, and mild conditions.

Automated summary

In this study, a highly selective NIS-promoted amino-diazidation and amino-iodoazidation of O-homoallyl benzimidates with NaN3 was reported. The method allows for the direct synthesis of a variety of vicinal diazido-substituted 1,3-oxazines and vicinal iodoazido-substituted 1,3-oxazines in a controlled manner.