Photooxidations and Related Reactions

单线态氧与硫化物、硫酸盐、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)扩大对氧化反应的机理的理解；2)开发和利用新型氧化剂；3)新型底物的氧化，这将为潜在有用材料的形成提供新的合成方法。在这一研究过程中，我们将研究相邻基团对硫化物光氧化的影响，考察过硫酸和氢过氧呋喃的合成和性质，并研究这些新型氧化剂向杂原子和不饱和底物转移氧的能力。来自有机动力学项目的这笔拨款支持怀俄明大学爱德华·克伦南教授的继续工作。在染料存在的情况下，分子氧可以暴露在高强度光下，产生氧的激发态，这被称为单线态氧。这种激发态物种是一种短寿命的反应分子，它会氧化各种有机分子。在这个项目中，我们将研究单线态氧与有机分子反应的详细步骤。此外，在某些氧化反应中产生的活性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上。这在合成独特的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.