COMPLEXITY-BUILDING ANNULATION REACTIONS WITH STRAINED RING BUILDING BLOCKS

用应变环积木构建复杂性环行反应

• 批准号: 1213082
• 负责人: Jeffrey Johnson
• 金额: $ 44.4万
• 依托单位: University of North Carolina at Chapel Hill
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-03-01 至 2017-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1213082&HistoricalAwards=false
• 关键词: COMPLEXITY; BUILDING; ANNULATION; REACTIONS; STRAINED

With this award, the Chemical Synthesis Program of the Chemistry Division is funding Professor Jeffrey Johnson of the Department of Chemistry at the University of North Carolina at Chapel Hill to develop new catalytic, enantioselective methods for the construction of heterocycles using readily accessible strained building blocks. Prior NSF-funded research has revealed a unique mechanism for tetrahydrofuran-forming annulation reactions between donor-acceptor cyclopropanes and aldehydes. From this point, other useful heterocycle constructions, including asymmetric variants, have been achieved. The mechanistic understanding gained to date is expected to drive the discovery of new reactions that allow simple access to structures not easily reached using existing methods. Examining new chemistry of donor-acceptor cyclopropanes and exploring the reactivity of heretofore unexplored donor-acceptor strained systems is expected to provide a diverse set of reaction products. A complete exploration of the useful yet underutilized "carbon as a nucleofuge" paradigm will lead to useful reaction patterns. Experimentation in these areas will also provide fertile ground for fundamental studies of reaction mechanism in transformations that involve ground state-destabilized building blocks. The development of a general platform for heterocycle construction using strained ring activation is of fundamental importance to organic and medicinal chemists. The exploration of myriad activation modes for the donor-acceptor substrates is likely to enhance adoption of the methodology in academic and industrial laboratories. Graduate student coworkers will become adept at a broad range of synthetic and analytical techniques that can be applied to a variety of problems. Through the continued inclusion of student researchers via the AVS Project SEED program, ethnic minorities that are historically underrepresented in the sciences will have access to cutting edge, yet tractable science.

有了这个奖项，化学部的化学合成计划正在资助查佩尔山的北卡罗来纳州大学化学系的杰弗里约翰逊教授开发新的催化，对映选择性的方法，用于使用容易获得的应变构建块构建杂环。 先前NSF资助的研究揭示了供体-受体环丙烷和醛之间形成四氢呋喃成环反应的独特机制。 从这一点出发，已经实现了其他有用的杂环结构，包括不对称变体。 迄今为止所获得的机械理解有望推动新反应的发现，这些反应允许简单地进入使用现有方法不容易达到的结构。 研究给体-受体环丙烷的新化学和探索迄今为止未探索的给体-受体应变系统的反应性，预计将提供一组不同的反应产物。 对有用但未充分利用的“碳作为离核剂”范例的完整探索将导致有用的反应模式。 这些领域的实验也将为涉及基态不稳定构建块的转换中的反应机制的基础研究提供肥沃的土壤。 发展一个利用张力环活化来构建杂环的通用平台对有机化学家和药物化学家来说是至关重要的。 探索供体-受体底物的无数激活模式可能会提高该方法在学术和工业实验室中的采用。 研究生同事将成为熟练的综合和分析技术，可以应用于各种问题的广泛范围。 通过AVS项目SEED计划继续纳入学生研究人员，历史上在科学领域代表性不足的少数民族将获得尖端但易于处理的科学。