Ultrafast time-resolved transient infrared and resonance Raman spectroscopic study of the photo-deprotection and rearrangement reactions of p-hydroxyphenacyl caged phosphates
Ultrafast time-resolved transient infrared and resonance Raman spectroscopic study of the photo-deprotection and rearrangement reactions of p-hydroxyphenacyl caged phosphates
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DOI：
10.1039/b908188g
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发表时间：
2010-01-01
影响因子：
3.4
通讯作者：
Xue, Jiadan
中科院分区：
文献类型：
--
作者：
Cao, Qian;Guan, Xiangguo;Xue, Jiadan
这是皮秒和纳秒时间分辨红外吸收光谱研究对羟基苯乙基二乙基磷酸(HPDP)在水溶液中的脱保护反应和随后的演化，以产生对羟基苯乙酸(HPAA)重排产物。这里报道的数据支持先前的超快荧光、拉曼和瞬时UV/可见光吸收研究，并为水在去保护反应中的作用提供了新的见解。它还提供了对三重态的初始形成及其与水的反应最终产生溶剂分离的离子和溶解反应产物HPAA之后发生的中间步骤的性质的洞察。此外，用密度泛函理论(DFT)方法研究了HPDP与水分子的三重态反应引起的去保护作用、接触离子对的形成以及随后导致HPAA重排产物的中间产物。基于时间分辨光谱实验和密度泛函理论计算结果，提出了更详细的反应机理。
This is a picosecond and nanosecond time-resolved infrared absorption spectroscopic study of p-hydroxphenacyl diethylphosphate (HPDP) in aqueous solution examining the deprotection reaction and subsequent evolution to produce the p-hydroxyphenylacetic acid (HPAA) rearrangement product. The data reported here support previous ultrafast fluorescence, Raman and transient UV/visible absorption studies and provide new insight into the role of water in the deprotection reaction. It also provides insight into the nature of the intermediate steps that take place following initial formation of the triplet state and its reaction with water to eventually produce the solvent-separated ions and solvolytic reaction product HPAA. In addition, density functional theory (DFT) calculations were performed to investigate the reactions of the triplet state of HPDP with water molecules to induce deprotection, the formation of a contact ion pair and the subsequent intermediates that lead to the HPAA rearrangement product. A more detailed reaction mechanism is proposed based on the time-resolved spectroscopy experiments and DFT computational results.