Department of Chemistry, University of Potsdam, Karl-Liebknecht-Strasse 24-25, 14476 Potsdam (Germany).
Chemistry. 2015 Jun 1;21(23):8569-77. doi: 10.1002/chem.201500146. Epub 2015 Apr 27.
Singlet oxygen donors are of current interest for medical applications, but suffer from a short half-life leading to low singlet oxygen yields and problems with storage. We have synthesized more than 25 new singlet oxygen donors based on differently substituted naphthalenes in only a few steps. The influence of functional groups on the reaction rate of the photooxygenations, thermolysis, half-life, and singlet oxygen yield has been thoroughly studied. We determined various thermodynamic data and compared them with density functional calculations. Interestingly, remarkable stabilities of functional groups during the photooxygenations and stabilizing effects for some endoperoxides during the thermolysis have been found. Furthermore, we give evidence for a partly concerted and partly stepwise thermolysis mechanism leading to singlet and triplet oxygen, respectively. Our results might be interesting for "dark oxygenations" and future applications in medicine.
单线态氧供体目前在医学应用中受到关注，但由于半衰期短，导致单线态氧产率低，储存问题也很严重。我们仅用几步就合成了 25 种以上基于不同取代萘的新型单线态氧供体。我们深入研究了官能团对光氧化反应速率、热解、半衰期和单线态氧产率的影响。我们测定了各种热力学数据，并与密度泛函计算进行了比较。有趣的是，我们发现，在光氧化反应中，官能团具有显著的稳定性，并且一些内过氧化物在热解过程中具有稳定作用。此外，我们还证明了一种部分协同和部分逐步的热解机制，分别导致单线态氧和三线态氧的生成。我们的研究结果可能对“暗氧化”和未来在医学中的应用具有重要意义。
