pH- and wavelength-dependent photodecarboxylation of ketoprofen.
pH- and wavelength-dependent photodecarboxylation of ketoprofen.
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DOI：
10.1021/ol202182k
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发表时间：
2011-09
期刊：
影响因子：
5.2
通讯作者：
Yanchang Xu;Xuebo Chen;W. Fang;D. Phillips
中科院分区：
文献类型：
--
作者：
Yanchang Xu;Xuebo Chen;W. Fang;D. Phillips
利用CASSCF/CASPT 2计算绘制了酮洛芬（KP）光脱羧反应的pH和波长依赖性路径。发现碱性形式（KP（-））的脱羧作用在330 nm处通过光激发填充时从长距离电荷转移（CT）激发态开始。在λ < 260 nm的光激发下，短距离CT激发态似乎是酸性形式（KP）脱羧的原因。H（2）O分子在反应中起着桥梁的作用，帮助质子转移。
The pH- and wavelength-dependent pathways for the photodecarboxylation of ketoprofen (KP) were mapped by CASSCF/CASPT2 computations. The decarboxylation of the basic form (KP(-)) was found to start from a long-distance charge transfer (CT) excited state when populated by photoexcitation at 330 nm. A short-distance CT excited state populated with photoexcitation at λ < 260 nm appears to be responsible for the decarboxylation of the acidic form (KP). The H(2)O molecules function as a bridge to assist proton transfer in the reactions examined here.