Mechanistic Studies of Free Radical Additions and Rearrangements

自由基加成和重排的机理研究

• 批准号: 9122531
• 负责人: Ned Porter
• 金额: $ 45.5万
• 依托单位: Duke University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1992
• 资助国家: 美国
• 起止时间: 1992-03-15 至 1995-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9122531&HistoricalAwards=false
• 关键词: Mechanistic; Studies; Free; Radical; Additions

An investigation of stereochemical control of free radical addition processes will be conducted. The overall goal of the research is to define the mechanism of free radical addition processes which results in exact control of the stereochemistry of the final products generated. Reactions to be investigated during the course of this project include radical additions, atom transfer, and polymerizations of alkenes bearing amide auxiliaries. Precise regulation of the tacticity of specifically engineered oligomers and polymers will be accomplished by use of very specific stereochemical reactions. The exact distribution of oligomers will be regulated by reactions in micellar environments designed to produce a discrete number of reaction steps. In addition, the chemistry of peroxyl radical rearrangement and cyclization reactions will be investigated by the use of stereochemical probes and oxygen isotopes. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor N. A. Porter at Duke University. The studies will center around efforts to engineer the exact structure of molecules by extremely efficient and selective free radical reactions. By forcing chemical reactions to take place in very specific pathways, it is possible to generate molecules that are designed to solve important problems by virtue of their carefully controlled structure. One of the final goals of this work is to make molecules which have many repeat units of exactly the same orientation in space. This will result in molecules with very unusual properties.

将对自由基加成过程的立体化学控制进行研究。这项研究的总体目标是确定自由基加成过程的机制，该过程导致对生成的最终产品的立体化学进行精确控制。本项目过程中要研究的反应包括自由基加成、原子转移和含酰胺助剂的烯烃聚合。通过使用非常特殊的立体化学反应，将实现对特定工程低聚物和聚合物的规整性的精确调节。齐聚物的准确分布将由胶束环境中的反应来调节，这些反应旨在产生不同数量的反应步骤。此外，还将使用立体化学探针和氧同位素来研究过氧基重排和环化反应的化学。来自有机动力学项目的这笔赠款支持杜克大学N·A·波特教授的继续工作。这些研究将围绕着通过极其高效和选择性的自由基反应来设计分子的准确结构的努力。通过迫使化学反应在非常特定的路径上发生，就有可能通过精心控制的结构产生旨在解决重要问题的分子。这项工作的最终目标之一是制造在空间中具有许多完全相同取向的重复单元的分子。这将导致分子具有非常不寻常的性质。