SYNTHESIS OF ELECTROCHEMICAL ENTITIES

该子项目是利用该技术的众多研究子项目之一 资源由 NIH/NCRR 资助的中心拨款提供。子项目和 研究者 (PI) 可能已从 NIH 的另一个来源获得主要资金， 因此可以在其他 CRISP 条目中表示。列出的机构是 对于中心来说，它不一定是研究者的机构。 由于电化学允许人们选择性地操纵分子的氧化态，产生反应性中间体，并反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，我们发现富电子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。这样，通常亲核烯醇化物等价物可以用作亲电子试剂。目前利用这种独特的翻转反应的努力主要集中在天然产物的构建上。 以类似的方式，我们正在利用电化学反转N-酰亚胺离子形成的正常极性的能力，以开发面向多样性的合成新方法，允许核心支架内的系统变化，以合成包含构象探针的受体靶向分子库，以快速收集有关受体三维需求的信息，并构建新的基于肽的生物缀合物。

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.