Photooxidations and Related Reactions

单线态氧与硫化物、亚磺酸盐、烯丙基锡烷和有机碲化合物的反应将被研究。这项研究的结果将有三个方面：1)扩大氧化反应的机理理解；2)新型氧化剂的开发利用；3)氧化新的底物，这将为潜在有用材料的形成提供新的合成方法。在本研究过程中，将研究邻基对硫化物光氧化的影响，并对过磺酸和氢过氧呋喃的合成和性质进行研究。这些新型氧化剂将氧转移到杂原子和不饱和底物的能力将被研究。来自有机动力学计划的这笔拨款支持怀俄明大学爱德华·克莱南教授的继续工作。分子氧可以暴露在有染料存在的高强度光下，产生激发态的氧，这被称为单线态氧。这种激发态分子是一种寿命较短的活性分子，能氧化各种有机分子。本课题将研究单线态氧与有机分子反应的具体步骤。此外，在某些氧化过程中产生的反应中间体将被用来以特定的方式将氧原子转移到其他有机分子中。这在合成独特分子方面具有潜在的应用前景。

Reactions of singlet oxygen with sulfides, sulfenates, allyl stannanes, and organotellurium compounds will be studied. The results of this research will be three-fold: 1) An expanded mechanistic understanding of oxidation reactions; 2) The development and utilization novel oxidizing agents; and 3) Oxidation of novel substrates that will provide new synthetic methods for the formation of potentially useful materials. In the course of this investigation, the effects of neighboring groups on sulfide photooxidations will be studied, the synthesis and properties of persulfenic acids and hydroperoxy sufuranes will be examined, and the ability of these new classes of oxidizing agents to transfer oxygen to heteroatoms and unsaturated substrates will be studied. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Edward Clennan at the University of Wyoming. Molecular oxygen can be exposed to high intensity light in the presence of a dye to generate an excited state of oxygen, which is referred to as singlet oxygen. This excited state species is a short-lived reactive molecule, which will oxidize various organic molecules. In this project, the detailed steps in the reaction of singlet oxygen with organic molecules will be studied. Furthermore, the reactive intermediates that are generated in certain of these oxidations will be used to transfer oxygen atoms to other organic molecules in a specific manner. This has potential application in the synthesis of unique molecules.