Catalytic transformations of oxygen- and nitrogen-containing substrates

在接下来的5年里，科顿集团将开发新的方法，单独使用可再生原料或与油基化学品结合使用来制造有机小分子和塑料。大多数可再生能源(二氧化碳、糖、氨基酸和相关的自然来源分子)含有氧和/或氮杂原子。这与从天然气、石油或煤炭中获得的化学品形成鲜明对比，这些化学品通常含有极少的非碳或氢原子。因此，需要新的化学方法，因为在过去的一个世纪，也就是石油时代，化学家们将他们的努力集中在将碳氢化合物选择性地转化为理想的产品上。由于化石燃料储备的枯竭，化学家现在必须努力有选择地将可再生原料转化为更高价值的产品。这意味着需要开发新的反应和新的催化剂。此外，利用二氧化碳作为新产品的起始材料是及时减少我们的碳足迹的关键研究领域。在科顿小组，为了实现这一目标，正在进行三个相互关联的研究：(1)来自生物质的新的含氮化学品及其反应性；(2)来自可再生原料的新的聚合物；(3)醇、醚、胺和酰胺的新的催化转化。在这些基础研究流中，有几个项目针对各国政府和研究组织强调的全球重要领域(例如，ACS绿色化学研究所圆桌会议，以及NSERC的战略领域，如可持续制造)：二氧化碳活化和利用、催化氧化反应和新的以氮为中心的化学。这些领域的进展可能会在未来15-30年内对加拿大的经济和环境产生重大影响。在可再生化学品领域，很少有研究人员同时针对小分子和聚合物目标，因此，由于这种双管齐下的组合方法，将会有新的重要发现。例如，我们从废弃的虾壳中制备的一种新的分子构建块，可能会导致生产一种具有类似芳纶(在防弹背心中发现的)性质的可再生聚合物。作为本研究计划的一部分，所发现的分子、材料和方法可用于生物活性化合物的全合成(医药)、高价值工程材料或商品塑料的生产(化学制造)，或作为未来研究和发现的垫脚石(知识库)。此外，还将培训大量的本科生和研究生(HQP)，他们将增加加拿大在旨在可持续发展和减少污染的技术领域的劳动力力量。科顿集团HQP被鼓励遵循绿色化学和工程的原则，同时获得基础化学问题解决和专业知识的培训。我们对机制驱动的研究感兴趣，因为HQP被要求获得他们发现和研究的化学过程的动力学和热力学数据。一旦获得这些数据，我们将努力利用这些信息在后续调查中改进最初的发现。在可能的情况下，原位FT-IR和核磁共振光谱测量是在“真实”反应条件下进行的，例如，HQP将利用我们改进的压力容器和ReactIR系统来研究二氧化碳的活化。作为这项研究计划的一部分，新发现最终将为加拿大和加拿大人带来经济和环境效益。

During the next 5 years, the Kerton group will develop new ways to make small organic molecules and plastics using renewable feedstocks alone or in combination with oil-based chemicals. Most renewables (carbon dioxide, sugars, amino acids and related naturally-sourced molecules) contain oxygen and/or nitrogen heteroatoms. This contrasts with chemicals obtained from gas, oil or coal that typically contain very few non-carbon or -hydrogen atoms. Therefore, new chemical methods are needed, because during the past century, “the petroleum age”, chemists have focused their efforts on selective conversion of hydrocarbons into desirable products. Due to depleting fossil fuel reserves, chemists must now strive to selectively convert renewable feedstocks into higher value products. This means that new reactions and new catalysts need to be developed. Furthermore, utilization of carbon dioxide as a starting material for new products is a crucial field of research for timely reductions in our carbon footprint. In the Kerton group, three inter-connected streams of research are being pursued towards this goal: (1) New nitrogen-containing chemicals from biomass and their reactivity; (2) New polymers derived from renewable feedstocks; and (3) New catalytic transformations of alcohols, ethers, amines and amides. Within these streams of fundamental research, several projects target global areas of importance highlighted by governments and research organizations (e.g. ACS Green Chemistry Institute Roundtables, and NSERC strategic areas such as Sustainable Manufacturing): carbon dioxide activation and utilization, catalytic oxidation reactions, and new nitrogen-centered chemistry. Advances in these areas could have a significant impact on Canada’s economy and environment in the next 15-30 years. Few researchers in the field of renewable chemicals are targeting both small molecule and polymer targets, therefore, due to this two-pronged combined approach, new and important discoveries will be made. For example, a new molecular building block, which we have prepared from waste shrimp shells, could lead to the production of a renewable polymer with properties similar to Kevlar (found in bullet-proof vests). Molecules, materials and methods discovered as part of this research program may find utility in the total synthesis of bioactive compounds (medicine), in the production of high-value engineering materials or commodity plastics (chemical manufacturing), or as a stepping-stone for future research and discoveries (knowledge base). Also, a large number of both undergraduate and graduate students (HQP) will be trained and they will add to the strength of Canada’s workforce in technological fields aimed at sustainable development and pollution reduction. Kerton group HQP are encouraged to follow the principles of green chemistry and engineering, whilst obtaining training in fundamental chemistry problem solving and expertise. We are interested in mechanism-driven research in that HQP are asked to obtain kinetic and thermodynamic data for the chemical processes that they discover and study. Once such data is obtained, we strive to use this information to improve on initial discoveries in subsequent investigations. Where possible, in situ FT-IR and NMR spectroscopic measurements are performed under ‘real’ reaction conditions e.g. HQP will make use of our modified pressure vessel and ReactIR system to study activation of carbon dioxide. New discoveries that are made as part of this research program will ultimately lead to economic and environmental benefits for Canada and Canadians.