A cooperative approach to iron-catalyzed C-H functionalization

铁催化C-H官能化的合作方法

• 批准号: 2481030
• 金额: --
• 依托单位: University of Manchester
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2020
• 资助国家: 英国
• 起止时间: 2020 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2481030
• 关键词: cooperative; approach; iron; catalyzed; functionalization

The development of predictable iron catalysis using well-defined catalysts systems offer the prospect to explore exciting and unique chemical reactivity not observed with canonical precious metals. This reactivity is essential for the advancement of synthetic chemistry and can be attributed to the unique properties of iron. One property which renders designing rational, well-defined catalysts challenging is the propensity of iron to form ill-defined structures under reaction conditions. This research program will deliver the tools necessary to overcome the ill-defined catalyst structures, through the synthesis of well-defined iron complexes centred on tailored boron-based Z-type ligands.This approach will be exemplified by the development of novel strategies for catalytic C-H functionalization, a waste-free route to high value products from low-cost and widely available starting materials. Despite the high interest, many challenges still remain in C-H functionalization chemistry, in particular, the application of 3d-metal catalysts. As a result of this challenge and despite the potential of iron-catalyzed C-H functionalizations, there is only a single example of iron-catalyzed C-H functionalization using well-defined complexes, highlighting this as a potentially fruitful and unexplored high impact areas of chemistry. The iron complexes we will utilize contain a weak sigma-type interaction from the metal to the boron and upon exposure to small molecules results in an oxidative addition across the M-B bond. This results in the borane becoming a borohydride by accepting the hydride and thereby facilitating a predictable, formal two electron process at iron. Initial investigations will establish the viability of these iron complexes towards the activation of C-H bonds in a range of substrates bearing different directing groups which are commonplace in precious-metal catalyzed C-H functionalization chemistry. Exploration will then turn to explore the scope of substrate coupling partners and subsequent catalysis. The development of enantioselective variants of the chemistry will also be a key consideration of the research. This will be achieved by synthesizing borane ligands from commercial chiral pool starting materials in a highly modular approach.This work is firmly in line with several EPSRC Priority Areas such as Catalysis and Novel and Efficient Chemical Synthesis and maps onto EPSRC "Dial-a-Molecule" Grand Challenge and onto other Priority Areas associated with "Manufacturing the Future" such as Chemical Reactions Dynamics and Mechanism, Chemical Biology and Healthcare Technologies: Diagnostics. Furthermore, the proposed research addresses the EPSRC Sustainable Chemistry Challenge, a key aspect for tomorrow's manufacturing processes.

可预测的铁催化的发展，使用明确的催化剂系统提供了前景，探索令人兴奋的和独特的化学反应性没有观察到与规范的贵金属。这种反应性对于合成化学的进步至关重要，并且可以归因于铁的独特性质。使设计合理的、明确定义的催化剂具有挑战性的一个性质是铁在反应条件下形成不明确结构的倾向。该研究计划将提供必要的工具，以克服不明确的催化剂结构，通过合成定义明确的铁配合物为中心的定制硼基Z型配体。这种方法将通过催化C-H功能化的新策略的开发来举例说明，这是一种从低成本和广泛可用的起始材料获得高价值产品的无废物路线。尽管有很高的兴趣，但在C-H官能化化学中仍然存在许多挑战，特别是3d-金属催化剂的应用。由于这一挑战，尽管铁催化的C-H官能化具有潜力，但只有一个使用明确定义的络合物的铁催化的C-H官能化的例子，突出了这是一个潜在的富有成效的和未开发的高影响力的化学领域。我们将利用的铁络合物含有从金属到硼的弱σ型相互作用，并且在暴露于小分子时导致M-B键上的氧化加成。这导致硼烷通过接受氢化物而变成硼氢化物，从而促进了可预测的、正式的铁双电子过程。初步研究将建立这些铁络合物对C-H键的活化的可行性，在一系列的基板轴承不同的导向基团，这是常见的贵金属催化的C-H官能化化学。然后，探索将转向探索底物偶联伴侣和后续催化的范围。化学的对映选择性变体的开发也将是研究的关键考虑因素。这将通过以高度模块化的方法从商业手性池起始材料合成硼烷配体来实现。这项工作完全符合EPSRC的几个优先领域，如催化和新颖有效的化学合成，并映射到EPSRC“Dial-a-Molecule”大挑战和与“制造未来”相关的其他优先领域，如化学反应动力学和机理，化学生物学和医疗保健技术：诊断。此外，拟议的研究解决了EPSRC可持续化学挑战，这是未来制造工艺的一个关键方面。