Harnessing the Power of Weak Bonds: Cleavage of N-O Bonds as Key Steps in Domino and Rearrangement Reactions of Functionalized Hydroxylamines

在化学系化学合成（SYN）项目的支持下，莱斯大学的László k<e:1> rti教授正在研究设计和开发新的生产含氮分子的简化方法。这些新方法为制造中间体和目标分子提供了潜在的更环保、更经济的选择，用于从农业、医药、分子电子学到21世纪材料的众多应用。新的分子转化利用了弱的氮氧（N-O）键，当这种键断裂时，会引发一系列精心安排的化学反应，也被称为多米诺骨牌反应。多米诺骨牌过程导致原始分子的骨架重新排列成全新的分子。这些类型的分子重排反应是化学已知的最有效和原子经济的过程之一。k<s:1> rti教授一直是莱斯大学化学乐趣分会的教师赞助商，该分会是一个扩展计划，其短期目标是建立一个强大的休斯顿地区卫星计划。长期目标是在德克萨斯州其他主要城市地区启动类似的卫星项目。这个外展计划为德克萨斯州的K-12学生提供了通过迷人的科学实验参与实验学习的机会。对科学的好奇心是通过有趣的示范，利用各种各样的角色模型来突出重要的教育课程。特别是，这个教育项目努力接触传统上未被充分代表的少数民族，并强调任何人都可以成为科学家！该计划的最终目标是激励年轻学生在科学、技术、工程和数学（STEM）领域从事职业。k<s:1> rti教授的研究小组将探索四种全新的多米诺反应策略，以生产小环和芳香杂环。这些转化的共同主题是底物或中间体的活化性质：通过它们的弱N-O键的断裂。根据不同的策略，这种N-O键切割触发或驱动特定的转化，包括新的环收缩和[3,3]-符号重排。制备高取代的含氮分子是合成有机化学中一项长期存在的挑战。提议的项目旨在解决这一挑战：通过切割N-O键提供的驱动力，可以简单地构建许多具有挑战性的含氮分子，包括目前未知的化学分子。这项提议的研究有望提供新的、可靠的、不含过渡金属的合成方法，作为传统方法的替代品，并有望对学术、政府和工业实验室的化学家产生影响。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Synthesis (SYN) program in the Division of Chemistry, Professor László Kürti of Rice University is studying the design and development of new streamlined methods for the production of nitrogen-containing molecules. These new methods offer potentially greener and more economical alternatives for manufacturing intermediates and target molecules for numerous applications ranging from agriculture, medicine, molecular electronics all the way to 21st century materials. The new molecular transformations exploit weak nitrogen-oxygen (N–O) bonds, which when ruptured, initiate carefully orchestrated sequences of chemical reactions, also known as domino reactions. The domino processes cause the skeletons of the original molecules to rearrange into completely new ones. These types of molecular rearrangement reactions are among the most efficient and atom-economical processes known to chemistry. Prof. Kürti has been a faculty sponsor of the Rice University chapter of Fun with Chemistry, an outreach program that has the short-term goal of establishing a robust Houston-area satellite program. The long-term goal is to initiate similar satellite programs in other major Texas metropolitan areas. This outreach program provides K-12 students in Texas with the opportunity to participate in experimental-learning through captivating science experiments. Curiosity for science is piqued through fun demonstrations that highlight important educational lessons by utilizing a variety of role models. In particular, this educational program strives to reach traditionally underrepresented minorities and highlight that anyone can be a scientist! The ultimate goal of the program is to inspire young students to pursue careers in science, technology, engineering, and mathematics (STEM)-fields.Professor Kürti’s research group will be exploring four fundamentally new domino reaction strategies to produce small-ring- and aromatic heterocycles. The common theme of these transformations is the nature of the activation of the substrates or intermediates: by a scission of their weak N–O bonds. Depending on the strategy, this N–O bond cleavage either triggers or drives the particular transformation, which include new ring-contractions and [3,3]-sigmatropic rearrangements. Making highly-substituted nitrogen-containing molecules is a long-standing challenge in synthetic organic chemistry. The proposed project aims to address this challenge: the driving force offered by cleaving N–O bonds enables the operationally simple construction of numerous challenging nitrogen-containing molecules, including ones currently unknown to chemistry. The proposed research promises to offer new, reliable, transition metal-free synthetic methods as alternatives to traditional approaches, and is expected to have impact on chemists in academic, governmental and industrial laboratories.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.