Olgun Mahire Emel, Menzek Abdullah, Şahin Ertan, Çetinkaya Yasin
Department of Chemistry, Faculty of Science, Atatürk University, Erzurum, Turkiye.
Department of Emergency Aid and Disaster Management, Faculty of Health Sciences, Ardahan University, Ardahan, Turkiye.
Turk J Chem. 2024 May 28;48(4):691-700. doi: 10.55730/1300-0527.3688. eCollection 2024.
Two 3-(-substituted phenyl)-3a,8a-dihydro-4-cyclohepta[d]isoxazoles were synthesized by 1,3-dipolar cycloaddition of the corresponding nitrile oxides with cycloheptatriene. Two endoperoxides were synthesized as facially selective and single products in high yields (93%-95%) from the reactions of isoxazole derivatives with singlet oxygen. The exact configurations of the endoperoxide with a methyl group in the phenyl ring and the diol synthesized from it were confirmed by X-ray analysis. To elucidate the mechanism, the formation energy of the endoperoxide was investigated by simulations using the software package Gaussian 09 and density functional theory calculations via the M06-2X/6-311+G(d,p) level method in dichloromethane. The results were consistent with experimental findings showing the formation of isoxazole products.
通过相应的腈氧化物与环庚三烯的1,3-偶极环加成反应合成了两种3-（-取代苯基）-3a,8a-二氢-4-环庚并[d]异恶唑。通过异恶唑衍生物与单线态氧的反应，以高产率（93%-95%）合成了两种内过氧化物，作为面选择性单一产物。通过X射线分析确定了苯环上带有甲基的内过氧化物及其合成的二醇的精确构型。为了阐明反应机理，使用Gaussian 09软件包进行模拟，并通过M06-2X/6-311+G(d,p)水平方法在二氯甲烷中进行密度泛函理论计算，对内过氧化物的生成能进行了研究。结果与显示异恶唑产物形成的实验结果一致。
