Exploration of New Reactivities for Sustainable Chemical Syntheses

背景与目的：化学合成通过转化自然资源，在生产药品、农用化学品、塑料、涂料、纺织品和电子材料方面起着至关重要的作用。然而，最先进的化学合成往往需要大量的辅助步骤，导致资源效率总体较低，并引起与化学废物有关的环境/健康问题。如何有效地利用有限的自然资源是未来可持续性的一个关键方面。该项目的总体目标是发现新的化学反应，以实现更可持续的未来化学合成，并在绿色/可持续合成化学的研究成果、影响和培训方面建立一个领先的卓越计划。研究计划：探索可以在环境条件下工作的新化学反应，最大限度地利用原子，并直接将自然资源（如可再生生物质）从其天然状态转化为有用的化学产品。在我们之前成功的基础上，利用我们最近激动人心的突破，这项发现资助将指导我们在以下四个主要途径的研究：(1)开发新的有机金属反应，不使用化学计量金属和有机卤化物；(2)探索芳香化合物光能反应的新途径；(3)开发木质素作为可再生的芳香族积木；(4)丰富的小分子（N2、CO2和甲烷）低温活化转化为高价值产品。意义：利用腙作为有机金属试剂替代品、无过渡金属芳香族取代和交叉偶联、酚类和木质素直接转化为芳香胺，以及少量惰性丰富物（N2、CO2和CH4）高效转化为高价值产物的联合成功，将从根本上改变化学教科书中所呈现的有机反应方法和化学家进行有机合成的方式。这些反应将大大提高化学合成的效率，并通过避免有机金属试剂的预合成和常见有机物的功能化-去功能化过程，以及芳香族产品的制造，最大限度地减少化学浪费。总之，这些将在金属、过渡金属、可再生芳烃和丰富的惰性分子利用方面的可持续性挑战中创造新的前沿。HQP培训：7 24 HQPπ的实验室(1个博士后,5博士,1本科学生)将直接参与在任何给定的年在这个提议,他将与综合研究技能训练有机合成、气相的反应,催化、光化学和纳米技术,核磁共振仪器专业,这个模型、TEM、SEM、TGA等和大约80 - 90 HQPs(未来5年)π的实验室将从这个发现相关培训项目中受益。

Background and Objectives: Chemical synthesis plays a vital role in producing pharmaceuticals, agrochemicals, plastics, coatings, textiles, and electronic materials by converting natural resources. However, state-of-the-art chemical synthesis often requires extensive auxiliary steps that lead to overall low resource efficiency and raise environmental/health concerns related to chemical waste. How to utilize limited natural resources efficiently constitutes a key aspect of future sustainability. The overall objective of this project is to discover new chemical reactivities for more sustainable future chemical syntheses and to establish a leading program of excellence in research output, impact, and training in Green/Sustainable Synthetic Chemistry. Research Plan: To explore new chemical reactivities that can work under ambient conditions, maximize atom-utilization, and directly transform natural resources such as renewable biomass from their native states into useful chemical products. Building on our previous successes and capitalizing our recent exciting breakthroughs, this Discovery Grant will direct our research in the following four major avenues: (1) To develop novel organometallic reactions without using stoichiometric metals and organic halides; (2) To explore new reaction pathways for aromatic compounds with photo energy; (3) To develop lignins as renewable aromatic building blocks; (4) Low-temperature activation and transformations of small abundant molecules (N2, CO2, and methane) into high valued products. Significance: The combined success of using hydrazones as organometallic reagent surrogates, transition-metal-free aromatic substitutions and cross couplings, direct conversion of phenols and lignins into aromatic amines, and efficient-conversion of small inert abundant (N2, CO2 and CH4) into high valued products will fundamentally change approaches to organic reactions as they are presented in chemistry textbooks and to the way chemists perform organic synthesis. These reactions will drastically increase the efficiency of chemical syntheses and minimize chemical waste by avoiding the presynthesis of organometallic reagents and functionalization-defunctionalization processes of common organics, as well as the manufacturing of aromatic products. Together, these will create new frontiers in sustainability challenges regarding metals, transition-metals, renewable aromatics and abundant inert molecules utilizations. Training of HQP: 7 out of 24 HQP in the PI's laboratory (1 postdoc, 5 PhDs, and 1 undergraduate student) will be directly involved at any given year in this proposal, who will be trained with comprehensive research skills in organic synthesis, gas-phase reactions, catalysis, photochemistry and nanotechnology, and instrumentation expertise in NMR, GCMS, TEM, SEM, TGA etc and approximately 80-90 HQPs (for the next 5 years) in the PI's laboratory will be benefited in related training from this Discovery Project.