Bicyclic-Constrained Alkyl Groups for Control of Reactivity

有机动力学项目的这笔拨款支持威斯康星大学麦迪逊分校的史蒂芬·F·尼尔森教授的研究。将研究四取代C=C、C=N、N=N、氧化N=N和三取代N=S官能团的氧化生成的自由基和阳离子。通过连续地从双键上去除一个和两个电子，将产生具有一个单位正电荷(自由基阳离子)和两个单位正电荷(指示)的物种。这些活性中间体作为几何函数的稳定性将通过将它们结合到双环中来追求。环大小的变化将允许作为环大小的函数的反应性的研究以及跨中等大小环的穿过空间的相互作用。将使用各种光谱和电化学技术来表征自由基阳离子和阳离子。ESR将是主要的光谱工具，将被用来阐明结构细节。在氧化条件下形成的活性中间体的生成、稳定和表征将促进对有机氧化反应的基本理解，并确定分子结构在促进或抑制氧化反应中的重要作用。

This grant in the Organic Dynamics Program supports the research of Professor Stephen F. Nelsen at the University of Wisconsin/Madison. Radical cations and dications generated by oxidation of tetrasubstituted C=C, C=N, N=N, oxygenated N=N, and trisubstituted N=S functionalities will be studied. By successive removal of one and two electrons from the double bonds, species with one unit of positive charge (radical cations) and two units of positive charge (dications) will be generated. The stability of these reactive intermediates as a function of geometry will be pursued by incorporating them into bicyclic rings. Variation of the ring size will permit an investigation of reactivity as a function of ring size and through-space interactions across medium sized rings. A variety of spectroscopic and electrochemical techniques will be used to characterize radical cations and dications. ESR will be the prime spectroscopic tool that will be used to elucidate structural details. The generation, stabilization, and characterization of reactive intermediates formed under oxidative conditions will advance the fundamental understanding of organic oxidation reactions and define the important role of molecular structure in facilitating or inhibiting oxidations.