SYNTHESIS OF ELECTROCHEMICAL ENTITIES

这个子项目是许多利用资源的研究子项目之一 由NIH/NCRR资助的中心拨款提供。子项目的主要支持 子项目的主要研究者可能是由其他来源提供的， 包括其它NIH来源。 列出的子项目总成本可能 代表子项目使用的中心基础设施的估计数量， 而不是由NCRR赠款提供给子项目或子项目工作人员的直接资金。 由于电化学允许人们选择性地操纵分子的氧化态，产生活性中间体，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导致形成有效捕获亲核试剂的自由基阳离子。以这种方式，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uppolung反应的努力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的能力，以扭转正常极性的N-酰基异氰尿酸离子的形成，以开发新的方法，以多样性为导向的合成，允许系统的变化内的核心支架，以合成受体靶向分子库，其中包含构象探针，用于快速收集信息的三维需求的受体，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. Primary support for the subproject and the subproject's principal investigator may have been provided by other sources, including other NIH sources. The Total Cost listed for the subproject likely represents the estimated amount of Center infrastructure utilized by the subproject, not direct funding provided by the NCRR grant to the subproject or subproject staff. 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.