Studies in Organosulfur Chemistry

有机硫化学研究

• 批准号: 8718024
• 负责人: Kyriacos C. Nicolaou
• 金额: --
• 依托单位: University of Pennsylvania
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-02-01 至 1989-09-01
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8718024&HistoricalAwards=false
• 关键词: Studies; Organosulfur; Chemistry

This research will lead to new methods of synthesizing complex molecules. It is being funded by the Organic and Macromolecular Chemistry Program. This work will permit the investigation of an unusual new class of molecules that contain the cyclic sulfur analog of cyclic peroxides. It has the potential to produce molecules with unusual chemical and biological properties. Four-membered rings with two adjacent sulfur atoms, known as 1,2-dithietanes, are of fundamental theoretical, chemical and biological interest. Although postulated as transient intermediates, no representative of this class of compounds was known as a stable compound until the recent disclosure of the first stable compound in this series, 1,2-dithiatopazine. The chemistry and biology of this compound will be investigated. A series of other 1,2 dithietanes will also be targeted for synthesis and those compounds proven stable will also be studied. The targeted systems were designed to probe the effect of molecular framework flanking the 1,2-dithietane moiety including the size of the adjacent rings and the presence of nitrogen and carbon in them. Molecular mechanics calculations will also be performed in attempts to predict the stability of designed systems. Several alternative methods for the synthesis of thionolactones will be explored. The chemistry of these intermediates will be studied with particular emphasis on new C-C bond forming reactions and cyclic ether formation. Thus, the intermolecular coupling of dithionolactones using electron transfer processes and subsequent chemistry will also be followed as a route to complex polycyclic systems. Dithionoesters will also be synthesized and their intramolecular coupling will be investigated as a means to construct cyclic frameworks. The reasons for the special stability of 1,2-dithiatopazine are not quite clear at present. Calculations on the stability of the systems are expected to lead to intesting predictions which will be tested experimentally. Also theoretical predictions regarding the physical, chemical and biological properties of these molecules are intriguing and will be put to the test. Furthermore, the power and scope to the projected methodology for the formation of the 1,2-dithietanes involving C-C bond formation could be important in ring construction. These fundamental reactions and other extensions involving the thionocarbonyl functionality will be investigated and have the potential of becoming useful synthetic methods.

这项研究将带来合成复杂分子的新方法。它是由有机化学和高分子化学项目资助的。这项工作将使一类不寻常的新分子的研究成为可能，这些分子含有环状过氧化氢的环硫类似物。它有可能生产出具有不同寻常的化学和生物特性的分子。具有两个相邻硫原子的四元环，称为1，2-二硫杂环，具有重要的理论、化学和生物学意义。虽然这类化合物被认为是过渡中间体，但直到最近该系列中第一个稳定的化合物1，2-二硫杂卓被披露之前，这类化合物的代表都不被认为是稳定的化合物。将对该化合物的化学和生物学进行研究。其他一系列1，2-二硫杂环戊烷也将作为合成的目标，那些被证明是稳定的化合物也将被研究。目标系统的设计是为了探索1，2-二硫杂环己烷部分侧翼的分子骨架的影响，包括相邻环的大小以及其中是否存在氮和碳。还将进行分子力学计算，以尝试预测所设计系统的稳定性。将探索几种合成硫代内酯的替代方法。将重点研究这些中间体的化学，特别是新的C-C键形成反应和环醚的形成。因此，利用电子转移过程和后续化学的分子间偶联也将作为复杂多环体系的一条途径。还将合成二硫代酯，并研究它们的分子内偶联作用，作为构建环状骨架的一种手段。1，2-二硫杂卓具有特殊稳定性的原因目前尚不十分清楚。对系统稳定性的计算预计将导致验证预测，这些预测将在实验中得到检验。关于这些分子的物理、化学和生物特性的理论预测也很耐人寻味，将受到考验。此外，涉及C-C键形成的1，2-二硫杂环乙烷的预测方法的能力和范围在环结构中可能是重要的。这些基本反应和其他涉及硫代羰基官能团的延伸将被研究，并有可能成为有用的合成方法。