alpha-Acidities of conformationally constrained sulfides, sulfoxides and sulfones

构象受限的硫化物、亚砜和砜的α-酸度

• 批准号: 232447543
• 负责人: Professor Dr. Joachim Podlech
• 金额: --
• 依托单位: Institut für Organische Chemie (IOC)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2012
• 资助国家: 德国
• 起止时间: 2011-12-31 至 2015-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/232447543?language=en
• 关键词: alpha; Acidities; conformationally; constrained; sulfides

Knowledge of structural properties and stabilities of chemical compounds is essential for the understanding of the compound´s reactivities and would allow for the development of new synthetic methods. The reactivity of chemical compounds is significantly ruled (inter alia) by their acidities. We will determine the acidities of sulfides, sulfoxides, and sulfones by measurement and by quantum chemical calculations and will reveal the reasons for these acidities. By utilization of conformationally constrained substrates we will be able to determine, which influence comes from an orientation of the functional groups relative to the respective acidic protons. This knowledge is especially relevant for the development of stereoselective reactions. The synthesis of these conformationally constrained compounds is part of this project; we plan to focus on 1,3-dithiane and 2-thiaadamantane derivatives. We will optimize and use an existing method for the measurement of the acidities based on a titration in the presence of UV indicators. The acidities will be calculated using DFT methods; they will be rationalized with natural bond orbital (NBO) and isodesmic calculations.

了解化合物的结构特性和稳定性对于理解化合物的反应性至关重要，并将有助于开发新的合成方法。化合物的反应性（阿利亚）受其酸度的影响。我们将通过测量和量子化学计算确定硫化物、亚砜和砜的酸度，并揭示这些酸度的原因。通过利用构象约束的底物，我们将能够确定，其中的影响来自于官能团相对于各自的酸性质子的取向。这些知识对于立体选择性反应的发展尤其重要。这些构象受限的化合物的合成是这个项目的一部分，我们计划专注于1，3-二噻烷和2-thiaadamantane衍生物。我们将优化和使用现有的方法来测量酸度的基础上，在紫外指示剂的存在下滴定。酸度将使用DFT方法计算;它们将用自然键轨道（NBO）和等键计算合理化。