Department of Chemistry, Faculty of Sciences and Arts, Ordu University, 52200, Ordu, Turkey.
Carbohydr Res. 2022 Dec;522:108681. doi: 10.1016/j.carres.2022.108681. Epub 2022 Sep 21.
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)PdCHCl] 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, H NMR, C NMR, COSY (2D-NMR), HRMS, and Elemental Analysis techniques.
首次报道了新型双同型二氯肌醇的合成，其构型与康杜糖醇-D 相似。使用环辛四烯作为起始分子的顺式二氯二烯的光氧化作用提供了三环内过氧化物。内过氧化物用硫脲还原得到相应的烯丙基顺式二醇。烯丙基顺式二醇与对甲苯磺酰基异氰酸酯形成双氨基甲酸酯基团，随后在三甲基硅基叠氮化物存在下用[(dba)PdCHCl]，得到新的单氨基甲酸酯以及恶唑烷酮衍生物。用四氧化锇氧化单氨基甲酸酯中的双键，然后进行乙酰化，得到所需的单氨基甲酸酯三乙酸酯。最后，通过甲醇中碳酸钾水解和单氨基甲酸酯基团的乙酰化，以高产率得到所需的卤代双环[4.2.0]肌醇（双同型二氯肌醇）。通过傅里叶变换红外光谱（FT-IR）、核磁共振氢谱（H NMR）、核磁共振碳谱（C NMR）、二维核磁相关谱（COSY 2D-NMR）、高分辨率质谱（HRMS）和元素分析技术对所有合成化合物进行了表征。
