Exploration of New Reactivities for Sustainable Chemical Syntheses

背景和目标： 化学合成在通过转化自然资源来生产药品、农用化学品、塑料、涂料、纺织品和电子材料方面发挥着至关重要的作用。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，并引发与化学废物有关的环境/健康问题。如何有效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为更可持续的未来化学合成发现新的化学反应，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的化学反应，最大限度地提高原子利用率，并将自然资源，如可再生生物质，从其原生状态直接转化为有用的化学产品。在我们以往成功的基础上，并充分利用我们最近取得的令人振奋的突破，这项发现拨款将指导我们在以下四个主要方面的研究：(1)开发新型有机金属反应，而不使用化学计量金属和有机卤化物；(2)探索具有光能的芳香化合物的新反应途径；(3)开发木质素作为可再生的芳香族构件；(4)低温活化并将丰富的小分子(氮气、二氧化碳和甲烷)转化为高价值产品。 重要意义： 将肼作为有机金属试剂替代品、不含过渡金属的芳香取代和交叉偶联、将酚和木质素直接转化为芳胺，以及将小的惰性丰度(氮气、二氧化碳和甲烷)高效转化为高价值产品的共同成功，将从根本上改变化学教科书中介绍的有机反应的方法和化学家进行有机合成的方法。这些反应将极大地提高化学合成的效率，避免有机金属试剂的预合成和常见有机物的官能化-去功能化过程，以及芳香族产品的制造。总而言之，这些将在金属、过渡金属、可再生芳烃和大量惰性分子利用方面的可持续性挑战方面创造新的前沿。 HQP培训： PI实验室的24名HQP中有7名(1名博士后、5名博士后和1名本科生)将在任何一年直接参与本计划，他们将接受在有机合成、气相反应、催化、光化学和纳米技术方面的综合研究技能培训，以及在核磁共振、GCMS、透射电子显微镜、扫描电子显微镜、热重分析等方面的仪器专业知识，PI实验室的约80-90名HQP(未来5年)将从本发现项目的相关培训中受益。

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.