Anionic and Pericyclic Reaction Cascades for Organic Synthesis

用于有机合成的阴离子和周环反应级联

基本信息

批准号：
2153657
负责人：
Jon Njardarson
金额：
$ 52.5万
依托单位：
University of Arizona
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2022
资助国家：
美国
起止时间：
2022-09-01 至 2025-08-31
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2153657&HistoricalAwards=false
关键词：
Anionic Pericyclic Reaction Cascades Organic

项目摘要

With the support of the Chemical Synthesis Program in the Division of Chemistry, Professor Njardarson of The University of Arizona is studying new classes of chemical reactions that will lead to more efficient methods for the manufacture of compounds of importance to society, such as pharmaceutical agents, agrochemicals, and advanced materials. The insights gained from the studies, which will encompass powerful multiple bond-forming 'cascade' reactions capable of rapidly generating all manner of molecules of interest, are anticipated to inform on the future practice of synthetic design. The broader impacts of the funded project also include the education and training of the student coworkers taking part in the research and extend to enabling Prof. Njardarson's continued development of innovative and freely accessible educational content for the general public. In this regard, the award will support an expansion to the content available on the PI's popular app and website 'Chemistry By Design (CByD)', with concurrent transformation of current and future content to a machine-readable format that should be compatible with emerging artificial intelligence/informatics technologies in the chemical synthesis field. The well-established "Top 200" family of posters form the Njardarson group on the structures and properties of pharmaceutical drugs will continue to be produced and made available annually in traditional and new custom content formats.This project will involve continued and significantly expanded investigations of the new class of counterion-dependent anionic asymmetric amino-Cope rearrangements recently introduced by the Njardarson group. This versatile reaction platform affords access to a range of complex enantioenriched chiral products (both cyclic and acyclic molecules) from readily available starting materials; however, much remains to be learned about its scope before the power of the approach can be fully realized. New work will include establishing methods for the selective trapping and exploitation of chiral enamide intermediates and studying the many possible in situ cyclization scenarios. These efforts will also include novel ways to streamline synthesis of the requisite amino-Cope precursors (conjugated chiral imines) while also exploiting the discovery of new useful cascades that may outcompete the amino-Cope reaction. The second part of the funded project is focused on the development of new transformations for the assembly of high value densely substituted aromatic structures such as pyridines, isoquinolines, and other arenes, from simple acyclic building blocks via pericyclic-centered reaction cascades. It is anticipated that a number of significant new and useful methods for the elaboration of sought after acyclic and cyclic products from simple starting materials, will emerge from the research program.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学合成计划中，在化学部的支持下，亚利桑那大学的Njardarson教授正在研究新的化学反应，这将导致更有效的方法来制造对社会重要性的化合物，例如药物，农业化学物质和高级材料。从研究中获得的见解，这些研究将涵盖能够快速产生各种感兴趣的各种分子的强大多种键形成的“级联反应”，以了解合成设计的未来实践。资助项目的更广泛的影响还包括对研究的学生同事的教育和培训，并扩展到使Njardarson教授持续开发创新性和自由访问的教育内容。在这方面，该奖项将支持扩展PI流行应用程序和网站“设计化学（CBYD）”上可用的内容，并同时将当前和将来的内容转换为机器可读格式，该格式应与化学合成领域中新兴的人工智能/信息技术兼容。 Njardarson组成的良好成就的“ Top 200”海报家族将继续生产并以传统和新的自定义内容格式生产并提供每年的产品。该项目将涉及持续的，并大大扩展对新的反依赖性氨基氨基氨基氨基氨基氨基氨基氨基氨基调重新安装组的研究。这个多功能反应平台可从随时可用的起始材料中获取一系列复杂的对映射手性产品（循环和无环分子）。但是，在完全实现该方法的力量之前，还需要了解其范围。新作品将包括建立用于选择性诱捕和剥削手性磁扰中间体的方法，并研究许多可能的原位环化场景。这些努力还将包括简化所需氨基代码前体（共轭手性胺）合成的新方法，同时还利用了发现新有用的级联反应的发现，这些级联反应可能胜过氨基反应。资助项目的第二部分重点是开发新的转化，用于组装高价值替代的芳香族结构，例如吡啶，等喹啉和其他领域，从简单的无环构建块通过Pericyclic Cericyclic中心的反应级联。可以预料，将从研究计划中出现许多重要的新有用方法，用于从简单的起始材料中阐述所追求的无环和环状产品。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛影响的审查标准来通过评估来支持的。