Bicyclic-Constrained Alkyl Groups for Control of Reactivity

这项有机动力学计划的拨款支持威斯康星大学/麦迪逊分校斯蒂芬·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官能团氧化产生的自由基阳离子和指示。通过从双键中连续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）的物质。这些反应性中间体的稳定性作为几何函数将通过将它们合并到双环中来追求。环尺寸的变化将允许研究反应性作为环尺寸的函数和跨中等大小环的空间相互作用。各种光谱和电化学技术将用于表征自由基阳离子和指示。ESR将是用于阐明结构细节的主要光谱工具。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.