SYNTHESIS OF ELECTROCHEMICAL ENTITIES

这个子项目是许多研究子项目中利用 资源由NIH/NCRR资助的中心拨款提供。子项目和 调查员(PI)可能从NIH的另一个来源获得了主要资金， 并因此可以在其他清晰的条目中表示。列出的机构是 该中心不一定是调查人员的机构。 由于电化学可以选择性地操纵分子的氧化状态，生成活性中间体，并逆转已知官能团的极性，因此它为发现和探索许多新的、合成上有用的反应提供了理想的方法。 例如，我们已经发现，富含电子的烯烃的阳极氧化会导致自由基阳离子的形成，从而有效地捕获亲核试剂。通过这种方式，通常亲核烯醇酸的等价物可以用作亲电剂。目前利用这种独特的Upolung反应的努力集中在天然产品的构建上。 以类似的方式，我们正在利用电化学的能力来逆转N-酰亚胺离子形成的正常极性，以便开发新的面向多样性的合成方法，允许在核心支架内进行系统的变化，以合成包含构象探针的受体靶向分子文库，用于快速收集关于受体三维要求的信息，并构建新的基于多肽的生物偶联物。

This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. Because electrochemistry allows one to selectively manipulate the oxidation state of molecules, create reactive intermediates, and reverse the polarity of known functional groups, it provides and ideal method for discovering and exploring many new, synthetically useful reactions. For example, we have found that the anodic oxidation of electron-rich olefins leads to the formation of radical cations that efficiently trap nucleophiles. In this way, normally nucleophilic enolate equivalents can be used as electrophiles. Current efforts to exploit this unique umpolung reaction are focusing on the construction of natural products. In a similar fashion, we are taking advantage electrochemistry's ability to reverse the normal polarity of N-acyliminium ion formation in order to develop new approaches to diversity-oriented synthesis that allow for systematic variations within a core scaffold to synthesize receptor-targeted molecular libraries that contain conformational probes for rapidly gathering information about the three dimensional requirements of the receptor, and to construct new peptide-based bioconjugates.