Developing Catalytic Methods to Control Cationic Electrocyclizations

开发控制阳离子电环化的催化方法

• 批准号: 1152725
• 负责人: Alison Frontier
• 金额: $ 43.5万
• 依托单位: University of Rochester
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-09-01 至 2015-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1152725&HistoricalAwards=false
• 关键词: Developing; Catalytic; Methods; Control; Cationic

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.

在这个由化学部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教授将开发利用催化方法控制阳离子电环化反应活性和不同类型选择性的策略。具体来说，他们将尝试实现对几种电环化过程的催化、不对称控制，包括1)芳香/杂芳香Nazarov环化（反应活性相对较低的底物），2)新版本的阳离子Piancatelli环化（反应活性相对较高的底物），以及3)能够将平面底物转化为具有相邻四元中心的环戊酮产物的环化/重排序列。这第三个反应序列将用于enokipodin抗生素的合成。通过催化作用增加分子复杂性是在研究实验室之外创造具有潜在影响的新有用化合物的关键手段。此外，学生在本项目中进行的研究，从本科到博士后水平，与他们的教育和专业培训密切相关，并有效地推动他们成为独立的科学家。实验室活动、详细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，他们将作为所有项目参与者的联合顾问。这些努力将得到其他活动的补充，这些活动将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Not Voodoo网站上添加新的科学内容，以便向更孤立的实验室环境中的网站访问者传播专家的知识。在研究和交流的刺激下，这些创新活动增强了化学的吸引力，从而对所研究的科学的更广泛影响作出了重要贡献。