期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 83, 期 9, 页码 4948-4962出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.8b00738
关键词
-
资金
- JSPS KAKENHI [16H06193, 17K19221, 16H02413]
- Grants-in-Aid for Scientific Research [16H06193, 17K19221] Funding Source: KAKEN
Since the pioneering work by Macmillan, Yoon, and Stephenson, homogeneous photoredox catalysis has occupied a central place in new reaction development in the field of organic chemistry. While heterogeneous semi-conductor photocatalysis has also been studied extensively, it has generally been recognized as a redox option in inorganic chemistry where such photocatalysis is most often used to catalyze carbon carbon bond cleavage and not in organic chemistry where bond formation is usually the focal point. Herein, we demonstrate that titanium dioxide photocatalysis is a powerful redox option to construct carbon carbon bonds by using intermolecular formal [2 + 2] cycloadditions as models. Synergy between excited electrons and holes generated upon irradiation is expected to promote the overall net redox neutral process. Key for the successful application is the use of a lithium perchlorate/nitromethane electrolyte solution, which exhibits remarkable Lewis acidity to facilitate the reactions of carbon-centered radical cations with carbon nucleophiles. The reaction mechanism is reasonably understood based on both intermolecular and intramolecular single electron transfer regulated by an aromatic redox tag. Most of the reactions were completed in less than 30 min even in aqueous and/or aerobic conditions without the need for sacrificial reducing or oxidizing substrates generally required for homogeneous photoredox catalysis.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据