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金催化氧化反应的thioalkynes与昆林N-氧化物:一个DFT研究
Wanying Zhang1,2, Baoping Ling1, Siwei Bi1
1School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, People's Republic of China.
密度函数理论 (DFT) 的计算揭示了类和类N-氧化物之间的金催化氧化反应. 在产品形成过程中,Cβ氧化途径比Cα氧化略有优势.
科学领域:
- 有机化学 有机化学
- 计算化学的计算化学
背景情况:
- 黄金催化在现代有机合成中至关重要.
- 奎诺林N-氧化物是多功能氧化剂和指导组.
- 在催化中,Thioalkynes提供了独特的反应性概况.
研究的目的:
- 阐明黄金催化氧化反应的机制,其中涉及thioalkynes和quinoline N-oxides.
- 为了比较氧化重组和氧化基化过程的机械路径.
- 为了确定关键的中间体和核友攻击网站.
主要方法:
- 使用密度函数理论 (DFT) 的计算.
- 反应路径的计算建模.
- 过渡状态和中间体的分析.
主要成果:
- 发现 thioalkynes 的 Cβ 氧化与 Cα 氧化具有竞争力,在氧化重组中对 Cβ 氧化略有偏好.
- 对于氧化化,用林N-氧化物对乙烯的Cβ-氧化产生了3-基-1-基立 phenylthiopropan-2-one.
- 四个成员的硫中间体经历了通过核性攻击的环开放,由素N-氧化物,而不是水.
结论:
- DFT计算为金催化氧化转化提供了详细的机械洞察力.
- 硫基氧化反应的区域选择性受反应类型的影响.
- 在拟议的机制中,氨酸N-氧化物充当氧化剂和核爱者.
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