通过[3+2]环加成反应区域特异性地形成硝基甲基取代的3-苯基-4,5-二氢异恶唑。

Mirosław Barbara, Babyuk Dmytro, Łapczuk-Krygier Agnieszka, Kącka-Zych Agnieszka, Demchuk Oleg M, Jasiński Radomir

1Department of Crystallography, Maria Curie-Sklodowska University, Maria Curie-Sklodowska St 3, 20-031 Lublin, Poland.

2Institute of Biology, Chemistry and Bioresources, Chernivtsi National University, 2 Kotsyubynski Str., Chernivtsi, 58012 Ukraine.

Monatsh Chem. 2018;149(10):1877-1884. doi: 10.1007/s00706-018-2227-6. Epub 2018 Aug 20.

ABSTRACT

5-(Nitromethyl)-3-phenyl-4,5-dihydroisoxazole was obtained as a product of a high-yielding [3 + 2] cycloaddition reaction of in situ-generated benzonitrile -oxide and 3-nitroprop-1-ene. For the first time, the regiochemistry of this reaction was unambiguously proven by X-ray structural analysis. The quantum-chemical calculation performed at the M06-2X/6-31G(d) (PCM) theoretical level affords a basis for explaining the course of reaction as well as the nature of transition states. Next, further DFT calculations together with spectral data shed light on structural aspects of the product.

摘要

5-（硝基甲基）-3-苯基-4,5-二氢异恶唑是原位生成的苯甲腈氧化物与3-硝基丙烯发生高产率[3 + 2]环加成反应的产物。首次通过X射线结构分析明确证实了该反应的区域化学。在M06-2X/6-31G(d)（PCM）理论水平上进行的量子化学计算为解释反应过程以及过渡态的性质提供了依据。接下来，进一步的密度泛函理论计算以及光谱数据揭示了该产物的结构特征。