Specificity Orchestration in Alkynylation and Vinylation of C-H Bonds by Acetylenic and Olefinic Triflones

这项研究的重点是通过使用炔基和乙烯基三氟酮来实现二级和三级C-H键的直接烷基化和烯化。这项研究将试图确定反应的机理，开发用于复杂底物的区域特异性烯基化反应的焓匹配试剂，定义适当的保护基，以便在典型的更具反应性的官能团存在的情况下，使未活化的叔碳-氢键能够选择性的烷基化，研究功能化的炔基三氟酮的反应，使用光学活性缩醛来合成对映体1，3-和1，2-二醇，寻找低温引发烷基化反应的替代试剂，利用反应诱导自由基环化和裂解，并扩大反应的范围，包括自由基介导的烯化、二烯基化和裂解烯丙基化和烯丙基化。通过这一奖项，合成有机计划正在支持普渡大学化学系的菲利普·L·福克斯博士的研究。Fuchs教授将专注于开发将C-H键转化为C-C键的方法。这种方法依赖于被称为三氟化钠的试剂，将为合成化学家提供一种强大的工具，用来修饰有机分子。

The focus of this research is to achieve direct alkynylation and olefination of secondary and tertiary C-H bonds via the use of alkynyl and vinyl triflones. The research will attempt to define the mechanism of the reaction, to develop enthalpy-matched reagents for regiospecific alkynylation of complex substrates, to define appropriate protecting groups to enable selective alkynylation of unactivated tertiary C-H bonds in the presence of typically more reactive functional groups, to examine the reactions of functionalized alkynyl triflones, to use optically active acetals for the enantiospecific synthesis of acetylenic 1,3- and 1,2-diols, to seek seek alternate reagents for low temperature initiation of the alkynylation reaction, to use the reaction to induce radical cyclizations and fragmentations and to broaden the scope of the reaction to include radical-mediated olefination, dienylation, allenylation and allylation. With this award, the Synthetic Organic Program is supporting the research of Dr. Philip L. Fuchs of the Department of Chemistry at Purdue University. Professor Fuchs will focus his work on developing methodology by which to transform C-H bonds into C-C bonds. Such methodology, relying on reagents known as triflones, would provide synthetic chemists with a powerful tool with which to modify organic molecules.