Gandioso Albert, Palau Marta, Nin-Hill Alba, Melnyk Ivanna, Rovira Carme, Nonell Santi, Velasco Dolores, García-Amorós Jaume, Marchán Vicente
Departament de Química Inorgànica i Orgànica, Secció de Química Orgànica, IBUB (AG, VM) Universitat de Barcelona 08028 Barcelona Spain.
Institut de Química Teòrica i Computacional (IQTCUB) Universitat de Barcelona 08028 Barcelona Spain.
ChemistryOpen. 2017 May 5;6(3):375-384. doi: 10.1002/open.201700067. eCollection 2017 Jun.
We report the synthesis and photochemical properties of a series of dicyanocoumarinylmethyl (DEAdcCM)- and dicyanocoumarinylethyl (DEAdcCE)-based photocages of carboxylic acids and amines with absorption maximum around 500 nm. Photolysis studies with green light have demonstrated that the structure of the coumarin chromophore as well as the nature of the leaving group and the type of bond to be photocleaved (ester or carbamate) have a strong influence on the rate and efficiency of the uncaging process. These experimental observations were also supported by DFT calculations. Such differences in deprotection kinetics have been exploited to sequentially photolyze two dicyanocoumarin-caged model compounds (e.g., benzoic acid and ethylamine), and open the way to increasing the number of functional levels that can be addressed with light in a single system, particularly when combining dicyanocoumarin caging groups with other photocleavable protecting groups, which remain intact under green light irradiation.
我们报道了一系列基于二氰基香豆素甲基（DEAdcCM）和二氰基香豆素乙基（DEAdcCE）的羧酸和胺光笼合物的合成及其光化学性质，其最大吸收波长在500 nm左右。绿光光解研究表明，香豆素发色团的结构、离去基团的性质以及要光裂解的键的类型（酯或氨基甲酸酯）对去笼过程的速率和效率有很大影响。这些实验观察结果也得到了密度泛函理论（DFT）计算的支持。去保护动力学的这种差异已被用于顺序光解两种二氰基香豆素笼合模型化合物（如苯甲酸和乙胺），并为增加单个系统中可用光处理的功能水平数量开辟了道路，特别是当将二氰基香豆素笼合基团与其他在绿光照射下保持完整的光可裂解保护基团结合时。
