Iodine Catalyzed Cross-Coupling Reactions

项目摘要-碘催化的交叉偶联反应 拟议的研究旨在发现和开发经济，环保和用户友好的碘 用于合成关键化学键（碳-氮和碳- 碳键）、官能团（酰胺、酰亚胺和酮）和骨架（含氮 杂环如吡咯）。尽管在交叉偶联反应中投入了极大的兴趣和努力， 碘催化的交叉偶联的实例与介导的方案的数量相比仍然很少 过渡金属催化剂。该建议是基于我们的初步结果，酰基自由基物种是 在碘/过硫酸钾催化剂体系存在下容易由醛底物产生， 其参与与各种含氮亲核试剂的化合物的偶联反应。 在完成拟议的工作后，将实现三个具体目标：1）一个简易的碘 将开发用于制备酰胺和酰亚胺的催化碳-氮键形成方案; 2)通过自由基加成机理的碘催化的碳-碳键形成反应将 3）通过碘和第一行后过渡金属Co-形成碳-碳键反应， 将开发催化交叉偶联机制。新方法有望服务于关键的 合成和药物化学家在制备相应化学键方面的需求， 新疗法的框架。对所提出的碘催化机理的深入研究将是 进行，这是预期产生的建议碘催化的全面理解， 作为该领域未来研究的模板。此外，该提案将改善和加强 皇后学院的研究和教育基础设施。它不仅提供研究机会， 皇后学院本科生中少数民族学生人数不足， 培养有兴趣从事STEM研究事业的年轻一代科学家 学科

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.