Photoreaction of 4-(Bromomethyl)-7-(diethylamino)coumarin: Generation of a Radical and Cation Triplet Diradical during the C-Br Bond Cleavage
Photoreaction of 4-(Bromomethyl)-7-(diethylamino)coumarin: Generation of a Radical and Cation Triplet Diradical during the C-Br Bond Cleavage
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4-(溴甲基)-7-(二乙氨基)香豆素的光反应：C-Br 键断裂过程中自由基和阳离子三重态双自由基的生成
DOI：
10.1021/acs.orglett.2c00694
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发表时间：
2022
期刊：
影响因子：
5.2
通讯作者：
Abe Manabu
中科院分区：
文献类型：
--
作者：
Takano Ma-aya;Abe Manabu
7-二乙氨基-4-甲基香豆素(DEACM)衍生物被广泛用作耐光性保护基团。本文研究了以BR为离开基团的DEACM-BR的光解反应。结果表明，反应的主要途径是通过均相C-Br键断裂生成自由基。有趣的是，从碳阳离子中间体(即7-(二乙氨基)-4-甲基阳离子(C))的三重态C-T衍生的产物被鉴定，从而首次证实了FC-T的存在。
7-Diethylamino-4-methyl coumarin (DEACM) derivatives are widely used as photolabile protecting groups. In this study, the photolysis of DEACM-Br with Br as the leaving group was investigated. The main reaction path was found to be the generation of radicalDvia homolytic C–Br bond cleavage. Interestingly, products derived fromC-T, the triplet state of the carbocation intermediate (i.e., 7-(diethylamino)-4-methyl cation (C)), were identified, thereby confirming the existence ofC-Tfor the first time.