Developing Catalytic Methods to Control Cationic Electrocyclizations

在这个由化学系化学合成项目资助的项目中，罗切斯特大学化学系的Alison Frontier教授和Richard Eisenberg教授将开发策略，以控制使用催化方法的阳离子电环化反应中的反应性和不同类型的选择性。 具体而言，他们将尝试实现几类电环化过程的催化、不对称控制，包括1）芳香族/杂芳香族Nazarov环化（具有相对低反应性的底物），2）阳离子Piancatelli环化的新版本（具有相对高反应性的底物），和3）能够将平面底物转化为具有相邻季中心的环戊烯酮产物的环化/重排序列。 这第三个反应序列将用于enokipodin抗生素的合成。通过催化增加分子复杂性是创造新的有用化合物的关键手段，这些化合物的潜在影响超出了研究实验室。 此外，学生在这个项目上进行的研究，从本科到博士后水平，与他们的教育和专业培训密切相关，并有效地推动他们沿着成为独立科学家的道路。 实验室活动，详细的分析和新实验的制定构成了这两位教授之间真正合作的基础，他们将担任所有项目参与者的共同顾问。 这些努力将得到其他活动的补充，使学生研究人员受益，同时建立一个科学家社区。 特别是，将优先考虑在“不是巫毒教”网站上增加新的科学内容，以便在较孤立的实验室环境中向网站访问者传播专家的知识。 在研究和交流的推动下，这些创新活动增强了化学的吸引力，从而以重要的方式促进了所研究科学的更广泛影响。

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Alison Frontier and Professor Richard Eisenberg of the Department of Chemistry at the University of Rochester will develop strategies to control reactivity and different types of selectivity in cationic electrocyclizations using catalytic methods. Specifically, they will attempt to achieve catalytic, asymmetric control of several classes of electrocyclization processes, including 1) aromatic/heteroaromatic Nazarov cyclization (substrates with relatively low reactivity), 2) a new version of the cationic Piancatelli cyclization (substrates with relatively high reactivity), and 3) a cyclization/ rearrangement sequence able to convert a planar substrate into a cyclopentenone product with adjacent quaternary centers. This third reaction sequence will be employed in a synthesis of enokipodin antibiotics.Increasing molecular complexity through catalysis represents a key means of creating new useful compounds of potential impact beyond the research laboratory. Furthermore, the research that students conduct on this project, from the undergraduate to the postdoctoral level, connects intimately with their education and professional training, and moves them effectively along the path to becoming independent scientists. Laboratory activities, detailed analyses and the formulation of new experiments form the foundation of a true collaboration between these two professors, who will serve as co-advisors for all project participants. These efforts will be complemented by other activities that benefit student researchers while building a community of scientists. In particular, addition of new scientific content to the Not Voodoo website will be prioritized, to disseminate the knowledge of experts to website visitors in more isolated laboratory environments. These innovative activities, stimulated by research and communication, enhance the attractiveness of chemistry and thus contribute in an essential way to the broader impacts of the science studied.