The well-known electrochemical Shono oxidation of Boc-protected cyclic amines was revised. Boc-protected morpholine 1, which in described conditions gives the mixture of products, was used as model compound. The process was optimized for the synthesis of carbamate 3 in 500g from 1 synthetic run. The optimized procedure was applied to the multigram synthesis of carbamates 6-11. Further electrophilic functionalization of the carbamates leads to latent 1,3-bielectrophilic compounds type 12, which was subjected into classical heterocyclization with binucleophilic reagents. In a case of hydrazine the corresponding pyrazoles 13, decorated by unusual manner, were prepared. The proposed methodology appears straightforward tools for the design and synthesis of MedChem relevant building blocks. For example using commercially available cyclic α-aminoacids type 14 the 5 step synthesis leads to the formation of α-aminoacids 15 with different linkers between aminoacids fragment and pyrazole nuclei. In the report the scope and limitation of above mentioned methodology will be discussed.

Optimized semi-industrial electrochemical preparation of cyclic encarbamates and its application for the MedChem relevant building blocks synthesis

2019 Fall National Meeting

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