Thioacetal/thioketal moieties have been identified as responsive to reactive oxygen species (ROS). Despite its utility in a broad range of applications, the mechanism that underlies the ROS-induced cleavage of these moieties is not well understood. In this work, through a series of structure-property relationship studies such as Hammett correlation, we propose a mechanism or the oxidative cleavage of thioacetals and thioketals, where the thiolate components are converted to the corresponding disulfide product along with the formation of the respective aldehydes and ketones. The mechanism proposed here involves thioether oxidation that leads to the formation of a thionium intermediate, hydrolysis of which leads to the aldehyde/ketone product. In addition, we also show a preliminary demonstration of the utility of such an understanding, as it offers to sequentially release two distinct small molecules caged in a substrate using two contradictory stimuli, viz. oxidative and reductive conditions.

硫缩醛/硫代缩酮部分已被确定为对活性氧（ROS）有反应。尽管其在广泛的应用中具有实用性，但尚不十分了解ROS诱导的这些部分切割的机理。在这项工作中，通过一系列的结构-特性关系研究（例如哈米特相关性），我们提出了硫缩醛和硫缩酮的机理或氧化裂解，其中硫醇盐组分被转化为相应的二硫化物产物，并形成了相应的醛。和酮。本文提出的机理涉及硫醚氧化，该硫醚氧化导致形成硫鎓中间体，该硫鎓中间体的水解导致醛/酮产物。此外，我们还初步展示了这种理解的实用性，因为它提供了使用两个相互矛盾的刺激，即顺序释放笼罩在基质中的两个不同的小分子，即。氧化和还原条件。