Synthesis and hydrolysis of monocarbamate from allylic 1,4-dicarbamate: Bis-homodichloroinositol

Abstract

The synthesis of novel bis-homodichloroinositol with a configuration similar to that of conduritol-D is reported for the first time. The photooxygenation of cis-dichloro-diene obtained using cyclooctatetraene as the starting molecule afforted the tricyclic endoperoxide. The reduction of the endoperoxide with thiourea gave the corresponding allylic cis-diol. Formation of the bis-carbamate groups with p-TsNCO of allylic cis-diol followed by the [(dba)3Pd2CHCl3] in the presence of trimethylsilyl azide, gave a new monocarbamate as well as oxazolidinone derivative. Oxidation of the double bond in the monocarbamate with osmium tetraoxide followed by acetylation furnished the desired monocarbamate triacetate. Eventually, the desired halogenated bicyclo[4.2.0] inositol (bis-homodichloroinositol) were obtained in high yield by hydrolysis of the acetate groups and monocarbanate group by potassium carbonate in methanol. Characterization of all the synthesized compounds were performed by FT-IR, 1H NMR, 13C NMR, COSY (2D-NMR), HRMS, and Elemental Analysis techniques.