Iodine Catalyzed Cross-Coupling Reactions

项目总结-碘催化的交叉偶联反应 这项拟议的研究旨在发现和开发经济、环保和用户友好的碘 催化交叉偶联反应合成关键化学键(碳-氮和碳-氮) 碳键)、官能团(酰胺、亚胺和酮)和骨架(含氮 杂环化合物，如吡咯)。尽管在交叉偶联反应上投入了极大的兴趣和努力， 与介导的方案相比，碘催化的交叉偶联的例子仍然很少 通过过渡金属催化剂。这一建议是基于我们的初步结果，即酰基自由基物种是 在碘/过硫酸钾催化体系存在下容易从醛底物中生成， 它们参与与各种含氮亲核试剂的化合物的偶联反应。 在拟议的工作完成后，将实现三个具体目标：1)一种方便的碘 将开发用于制备酰胺和酰亚胺的催化碳-氮键形成协议； 2)碘通过自由基加成机理催化的碳-碳键形成反应 3)通过碘和第一排后过渡金属共生成碳-碳键的反应。 催化的交叉偶联机理将被开发出来。预计新方法将服务于关键的 合成化学家和药物化学家在制备相应的化学键和 新疗法的框架。将对所提出的碘催化机理进行彻底的调查 进行，预计将产生对拟议的碘催化和 作为今后该领域研究的模板。此外，该提案还将改善和加强 皇后学院的研究和教育基础设施。它不仅将为以下方面提供研究机会 皇后学院本科生中许多未被充分代表的少数族裔学生，但也将有所帮助 培养有志于在STEM从事研究事业的年轻一代科学家 纪律。

Project Summary – Iodine Catalyzed Cross-Coupling Reactions The proposed research aims to discover and develop economical, environmentally- and user-friendly iodine catalyzed cross-coupling reactions for the synthesis of key chemical bonds (carbon-nitrogen and carbon- carbon bonds), functional groups (amides, imides and ketones) and frameworks (nitrogen-containing heterocycles such as pyrrole). Despite the great interest and efforts devoted in cross-coupling reactions, examples of iodine catalyzed cross-coupling still remain scarce compared to the number of protocols mediated by transition metal catalysts. The proposal is grounded in our preliminary results that acyl radical species are readily generated from aldehyde substrates in the presence of an iodine/potassium persulfate catalyst system, which participate in coupling reactions with a variety of chemical compounds containing nitrogen nucleophiles. Upon the completion of the proposed work, three specific aims will be accomplished: 1) a facile iodine catalyzed carbon-nitrogen bond formation protocol for the preparation of amides and imides will be developed; 2) an iodine catalyzed carbon-carbon bond formation reaction via radical addition mechanism will be developed; 3) a carbon-carbon bond formation reaction via an iodine and first-row late transition metal co- catalyzed cross-coupling mechanism will be developed. The new methods are expected to serve the critical needs of synthetic and medicinal chemists in preparation of the corresponding chemical bonds and frameworks for novel therapeutics. A thorough investigation of the proposed iodine catalysis mechanism will be conducted, which is expected to yield a comprehensive understanding of the proposed iodine catalysis and serve as a template for future study in the field. In addition, the proposal will improve and strengthen the infrastructure of research and education at Queens College. It will not only provide research opportunities to the many underrepresented minority students among the Queens College undergraduates, but also will help nurture the young generation of scientists who are interested in pursuing a research career in the STEM disciplines.