Synthesis of Benzophenone Nucleosides and Their Photocatalytic Evaluation for [2+2] Cycloaddition in Aqueous Media
Synthesis of Benzophenone Nucleosides and Their Photocatalytic Evaluation for [2+2] Cycloaddition in Aqueous Media
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DOI：
10.1002/ejoc.201500885
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发表时间：
2015-10
影响因子：
2.8
通讯作者：
Nadine Gaß;H. Wagenknecht
中科院分区：
文献类型：
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作者：
Nadine Gaß;H. Wagenknecht
合成了四种与羰基有关的对位取代的二苯甲酮核苷（-NH 2、-NMe 2、-OMe和-Me），并通过它们的光学性质进行了表征。取代基的供电子性质影响了这些核苷的光学性质，特别是其UV/维斯吸收光谱中电荷转移带的红移。合成核苷在水溶液中的溶解度允许喹诺酮底物的光催化分子内[2+2]环加成反应通过用365 nm发光二极管（LED）灯照射混合物在H2O/MeCN中发生。使MeO-和Me-取代的二苯甲酮核苷以亚化学计量的量经受这些反应条件。延长照射时间后，底物转化与产物分解竞争。在我们的研究结果的基础上，我们确定，Me-取代的二苯甲酮核苷具有潜在的应用在发展中的光催化活性的DNA酶在体内的应用在化学生物学和对映选择性在水溶液中的酶。
Four benzophenone nucleosides that are para-substituted (–NH2, –NMe2, –OMe, and –Me) in relation to the carbonyl group were synthesized and characterized by their optical properties. The electron-donating character of the substituents influenced the optical properties of these nucleosides, especially the bathochromic shift of the charge-transfer band in their UV/Vis absorption spectra. The solubility of the synthetic nucleosides in aqueous solution allowed for a photocatalytic intramolecular [2+2] cycloaddition of a quinolone substrate to take place in H2O/MeCN by irradiating the mixture with 365 nm light-emitting diode (LED) lamps. The MeO- and Me-substituted benzophenone nucleosides were subjected to these reaction conditions in substoichiometric amounts. After prolonged irradiation times, substrate conversions competed with product decomposition. On the basis of our results, we determined that the Me-substituted benzophenone nucleoside has potential applications in the development of photocatalytically active DNAzymes for both in vivo applications in chemical biology and enantioselective photocatalysis in aqueous solutions.