通过极性翻转方法实现可见光诱导的醛的还原炔基化反应。
Visible Light-Induced Reductive Alkynylation of Aldehydes by Umpolung Approach.
作者信息
Tanaka Ibuki, Sawamura Masaya, Shimizu Yohei
机构信息
Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21 Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan.
出版信息
Org Lett. 2022 Jan 21;24(2):520-524. doi: 10.1021/acs.orglett.1c03927. Epub 2021 Dec 29.
Reductive alkynylation of aldehydes by the Umpolung approach was developed using a photoredox catalyst under blue LED irradiation. Ketyl radicals, generated by single-electron reduction of aldehydes through proton-coupled electron transfer (PCET), reacted with electrophilic alkynylsulfones. Sterically demanding bulky aldehydes reacted smoothly under the Umpolung reaction conditions. Moreover, the alkynylation proceeded chemoselectively with an aryl aldehyde group in the presence of other carbonyl groups including an aliphatic aldehyde group.
通过极性翻转方法，在蓝色发光二极管照射下使用光氧化还原催化剂实现了醛的还原炔基化反应。醛通过质子耦合电子转移（PCET）进行单电子还原生成的酮基自由基与亲电炔基砜发生反应。位阻较大的醛在极性翻转反应条件下顺利反应。此外，在包括脂肪醛基在内的其他羰基存在下，炔基化反应对芳醛基具有化学选择性。
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