Importance of Singlet Oxygen in Photocatalytic Reactions of 2-Aryl-1,2,3,4-tetrahydroisoquinolines Using Chalcogenorosamine Photocatalysts
Importance of Singlet Oxygen in Photocatalytic Reactions of 2-Aryl-1,2,3,4-tetrahydroisoquinolines Using Chalcogenorosamine Photocatalysts
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DOI：
10.1021/acs.organomet.9b00126
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发表时间：
2019-06
期刊：
影响因子：
2.8
通讯作者：
J. Clark;Jacqueline E. Hill;Irving D. Rettig;Joshua J. Beres;R. Ziniuk;Tymish Y. Ohulchanskyy;T. McCormick;M. Detty
中科院分区：
文献类型：
--
作者：
J. Clark;Jacqueline E. Hill;Irving D. Rettig;Joshua J. Beres;R. Ziniuk;Tymish Y. Ohulchanskyy;T. McCormick;M. Detty
使用硫族胺光催化剂和 LED 照射，实现了 2-芳基-1,2,3,4-四氢异喹啉的有氧氧化。使用硒代胺和碲胺光催化剂，这些底物与硝基甲烷之间的光催化氮杂亨利反应比使用硫代胺和玫瑰胺光催化剂更有效，这与光催化剂产生单线态氧（1O2）的倾向相对应。适当地，当反应在氮气气氛下进行时，光催化氮杂亨利反应的产率大大降低。在 2% 乙腈水溶液中，用硒胺和碲胺光催化剂将 2-芳基-1,2,3,4-四氢异喹啉氧化成相应的 2-芳基-3,4-二氢异喹诺酮 13a-13c。二-2-芳基-1,2,3,4-四氢异喹啉-1-基过氧化物14a和14b被证明是该反应中的中间体。硫代胺光催化剂在照射时确实会产生 1O2，但不会产生 2-芳基-3,4-二氢异喹啉...
Aerobic oxidation of 2-aryl-1,2,3,4-tetrahydroisoquinolines was achieved photocatalytically using chalcogenorosamine photocatalysts and LED irradiation. The photocatalytic aza-Henry reaction between these substrates and nitromethane was more efficient with selenorosamine and tellurorosamine photocatalysts than with thiorosamine and rosamine photocatalysts, corresponding to the propensity of the photocatalysts to generate singlet oxygen (1O2). Appropriately, yields for the photocatalytic aza-Henry reaction were greatly reduced when the reactions were conducted under a nitrogen atmosphere. The 2-aryl-1,2,3,4-tetrahydroisoquinolines were oxidized to the corresponding 2-aryl-3,4-dihydroisoquinolones 13a–13c with selenorosamine and tellurorosamine photocatalysts in 2% aqueous acetonitrile. Di-2-aryl-1,2,3,4-tetrahydroisoquinolin-1-yl peroxides 14a and 14b were shown to be intermediates in this reaction. Thiorosamine photocatalysts, which do generate 1O2 upon irradiation, did not give 2-aryl-3,4-dihydroisoquino...