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生产药物、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，导致总体资源效率低下，并引起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性，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计划。 研究计划： 探索新的化学反应，可以在环境条件下工作，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。 在过去的成功基础上，并利用我们最近取得的令人兴奋的突破，这项发现资助将把我们的研究引向以下四个主要方向：（1）开发不使用化学计量金属和有机卤化物的新型有机金属反应;（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结构单元;（4）开发新的有机金属化合物。（4）低温活化并将丰富的小分子（N2、CO2和甲烷）转化为高价值产品。 重要性： 使用腙作为有机金属试剂替代物、不含过渡金属的芳族取代和交叉偶联、酚和木质素直接转化为芳族胺以及少量惰性物质（N2、CO2和CH 4）有效转化为高价值产品的综合成功将从根本上改变化学教科书中所介绍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官能化-去官能化过程以及芳香族产品的制造来最大限度地减少化学废物。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： PI实验室24名HQP中的7名（1名博士后，5名博士和1名本科生）将直接参与本提案的任何一年，他们将接受有机合成，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NMR，GCMS，TEM，SEM，TGA等和PI实验室中的大约80-90名HQP（未来5年）将受益于本发现项目的相关培训。

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.