由DMSO稳定的素和素离子池. 适用于基二功能的多功能试剂
Yosuke Ashikari1, Akihiro Shimizu, Toshiki Nokami
1Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University , Kyotodaigaku-Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
电化学氧化产生了稳定的素和素离子. 这些是有机合成中的多功能试剂,使各种功能化有机化合物的形成成为可能.
科学领域:
- 电化学 电化学 电化学
- 计算化学计算化学
- 有机合成 有机合成
背景情况:
- 和酸盐是有反应性的物种.
- 这些离子的稳定对于它们的应用至关重要.
- 甲基二硫氧化物 (DMSO) 是电化学研究中常见的溶剂.
研究的目的:
- 通过低温电化学氧化产生和稳定素和酸 (X+).
- 调查二甲基硫氧化物 (DMSO) 对这些阳离子的稳定作用.
- 探索这些稳定离子池在有机反应中的合成实用性.
主要方法:
- 低温电化学氧化用于阴子生成.
- 密度函数理论 (DFT) 计算用于稳定性分析.
- 冷喷离子质谱 (MS) 用于复杂的观测.
- 与烯,氨基烯和1,6-烯的反应,用于合成应用.
主要成果:
- 稳定的Br +,I +,ArS +和ArSe +离子池在DMSO中产生和积累.
- DFT的计算证实了DMSO通过协调的稳定作用.
- 通过MS观察到I+与DMSO的复合体.
- 确定了阴离子稳定性顺序: Br+ < I+ < ArS+ < ArSe+.
- 阴离子池与反应,形成β-X替代的氧硫离子,可转化为碳化合物或酒精.
- 用氨基和1,6-二烯来实现循环反应.
结论:
- 在DMSO中低温电化学氧化提供了一种产生和稳定活性素和素离子的方法.
- 通过协调,DMSO在稳定这些离子中发挥着关键作用.
- 生成的阴离子池是合成功能化有机分子的多功能试剂,包括碳化合物,酒精和循环产物.
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