铁 (III) 酸盐/TEMPO催化有氧酒精氧化:序列与集成氧化合作的区别
Jordan E Nutting1, Kaining Mao1, Shannon S Stahl1
1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.
Journal of the American Chemical Society
|July 7, 2021
概括
这项研究揭示了一种用于酒精氧化的新型铁/氨基催化剂系统,通过氧化还原级联表现出"连续合作性". 这与铜催化剂不同,在氧化反应中提供新的化学选择性.
科学领域:
- 催化剂
- 有机化学
- 无机化学
背景情况:
- 使用过渡金属和氨基的合作催化是酒精氧化的关键.
- 铜/氨基系统在酒精氧化中表现出"集成合作性".
- 铁/氨基系统具有独特的催化机制.
研究的目的:
- 研究一种用于有氧酒精氧化的新型铁/氨基催化剂系统的机制.
- 在铁催化系统中提供"连续合作"的证据.
- 为了比较铁基和铜基催化剂的机制差异.
主要方法:
- 有氧酒精氧化反应.
- 用于现场检测中间体的循环步骤时计.
- 铁酸盐启动的氧化还原循环的研究.
主要成果:
- 在Fe/aminoxyl系统中发现了"连续合作"的证据.
- 直接检测到一种oxoammonium物种作为氧化剂.
- 一个基于NO的氧化还原循环启动了氨基/胺的氧化到.
- 与Cu/ aminoxyl系统相比,观察到明显的化学选择性和功能组兼容性.
结论:
- 铁/氨基催化剂系统通过"连续合作",与/氨基系统的"集成合作"不同.
- 机理上的差异归因于铁酸启动的NO基氧化还原循环.
- 这为选择性酒精氧化提供了一个新的途径,具有量身定制的功能组耐受性.
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