Department of Chemical Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan.
Department of Applied Biological Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo 183-8509, Japan.
J Org Chem. 2023 May 5;88(9):5913-5922. doi: 10.1021/acs.joc.3c00293. Epub 2023 Apr 25.
Arene C-H aminations using catalytic amounts of a 2,3-dichloro-5,6-dicyano--benzoquinone (DDQ) photocatalyst are described. Benzene, which has an oxidation potential of 2.48 V (vs SCE), was functionalized by pyrazoles, triazoles, tetrazoles, purines, and -butoxycarbonyl amine. Arenes underwent amination via a combination of ultraviolet (UV) light and a DDQ photocatalyst without a typical co-oxidant. Although the mechanism remains an open question, DDQH, which is generated from DDQ after oxidation, is reactivated to DDQ under UV light irradiation conditions, possibly with the assistance of adventitious O and/or a solvent as the terminal oxidant(s) in this system.
使用催化量的 2,3-二氯-5,6-二氰基-1,4-苯醌（DDQ）光催化剂进行芳基 C-H 胺化反应。苯的氧化电位为 2.48 V（相对于 SCE），可以通过吡唑、三唑、四唑、嘌呤和叔丁氧羰基胺进行功能化。芳基通过紫外线（UV）光和 DDQ 光催化剂的组合进行胺化，而不需要典型的共氧化剂。尽管机制仍然是一个悬而未决的问题，但 DDQH 是 DDQ 氧化后产生的，在 UV 光照射条件下可以重新激活为 DDQ，可能在这个体系中，需要借助偶然的 O 和/或溶剂作为末端氧化剂。
