Exploration of New Reactivities for Sustainable Chemical Syntheses

探索可持续化学合成的新反应

• 批准号: RGPIN-2020-05659
• 负责人: Li, ChaoJun
• 金额: $ 5.76万
• 依托单位: McGill University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=747972
• 关键词: Exploration; New; Reactivities; Sustainable; Chemical

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.

背景和目标：化学合成在利用自然资源生产药品、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，最先进的化学合成通常需要大量的辅助步骤，导致整体资源效率较低，并引发与化学废物相关的环境/健康问题。如何有效地利用有限的自然资源是未来可持续发展的一个关键方面。该项目的总体目标是发现新的化学反应性，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：探索可在环境条件下工作的新化学反应性，最大限度地提高原子利用率，并将可再生生物质等自然资源从其原生状态直接转化为有用的化学产品。在我们之前的成功基础上，并利用我们最近令人兴奋的突破，这项发现资助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）探索芳香族化合物光能反应新途径； (3) 开发木质素作为可再生芳香原料； (4) 丰富的小分子（N2、CO2和甲烷）的低温活化和转化为高价值产品。 意义：使用腙作为有机金属试剂替代物、无过渡金属的芳族取代和交叉偶联、将酚和木质素直接转化为芳香胺以及将小量惰性物质（N2、CO2和CH4）有效转化为高价值产物的综合成功将从根本上改变化学教科书中介绍的有机反应方法以及化学家的操作方式 有机合成。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。这些将为金属、过渡金属、可再生芳烃和丰富的惰性分子利用等可持续发展挑战创造新的领域。 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）将直接参与本提案中的任何一年，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以及NMR、GCMS、TEM、SEM、TGA等方面的仪器专业知识的培训 PI实验室的80-90名HQP（未来5年）将受益于该发现项目的相关培训。