New Strategies and Reactions for the α-C–H Functionalization and Hydrofunctionalization of Carbon–Carbon Multiple Bonds

项目摘要 该项目的目标是开发一系列新的有机方法，通过非传统的 烯烃和烯烃的π键以及与之相关的丙叉基的活化途径 和多头的位置。这些方法极大地增加了这些官能团的多功能性，提供 简化了对与生物医学相关的化合物中经常出现的亚结构和基序的访问 研究。特别是，在第一个研究领域，我们开发了用于催化生成的铁基催化剂 亲核的炔丙基和烯丙基的等价物。这些催化中间体的生产将使 在各种合成有用和生物医学相关的背景下形成C-C和C-X键。在 第二个研究领域，我们开发了利用新发现的一系列试剂和 由炔烃生成缺电子乙烯基中间体的条件。这些试剂和 条件使乙烯基亲电化学在复杂的后期环境中得以发展 以立体定义的方式合成杂环衍生物和三取代烯烃。这些新方法 将使药物发现和开发工作加速进行，发挥积极的作用 对公众健康的影响。

Project Summary The objective of this project is the development of a series of new organic methods through nontraditional approaches for the activation of the π-bonds of alkynes and alkenes, along with their associated propargylic and allylic positions. These methods greatly increase the versatility of these functional groups, providing streamlined access to substructures and motifs that regularly occur in compounds of relevance to biomedical research. In particular, in the first research area, we develop iron-based catalysts for the catalytic generation of nucleophilic propargyl and allyl equivalents. The production of these catalytic intermediates will allow for the formation of C–C and C–X bonds in a variety of synthetically useful and biomedically relevant contexts. In the second research area, we develop methods that take advantage of a newly discovered series for reagents and conditions for the generation of electron-deficient vinyl intermediates from alkynes. These reagents and conditions enable the development of vinyl electrophile chemistry in complex, late-stage contexts for the synthesis of heterocyclic derivatives and trisubstituted olefins in a stereodefined manner. These new methods will allow for drug discovery and development efforts to take place in an accelerated manner to exert a positive impact on public health.