Synthesis and hydrolysis of monocarbamate from allylic 1, 4-dicarbamate: Bis-homodichloroinositol. (December 2022)

• Record Type: Journal Article
• Authors: Kelebekli, Latif
• Is Part Of: Carbohydrate research. Volume 522(2022)
• Publication Date: 2022-12
• Subjects: Monocarbamate -- Bis-carbamate -- Carbamate hydrolysis -- Carbamate-ester hydrolysis -- Bis-homodichloroinositol; Carbohydrates -- Periodicals; Chemistry, Organic -- Periodicals; Biochemistry -- Periodicals; Carbohydrates -- Periodicals; Chimie organique -- Périodiques; Glucides -- Périodiques; Biochemistry; Carbohydrates; Chemistry, Organic; Periodicals; Electronic journals; 507.78
• DOI: 10.1016/j.carres.2022.108681
• Languages: English
• ISSNs: 0008-6215

Abstract

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)3 Pd2 CHCl3 ] 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, 1 H NMR, 13 C NMR, COSY (2D-NMR), HRMS, and Elemental Analysis techniques. Graphical abstract: Image 1 Highlights: Efficient synthesis of monocarbamate from allylic 1, 4-dicarbamate Effect of TMSN3 on bis -carbamate. Synthesis of chloroinositol derivative similar to cis -inositol structure. A novel bis -homoinositol derivative was efficiently synthesized.