Asymmetric Catalysis Using Novel Iron Complexes.

使用新型铁配合物的不对称催化。

• 批准号: EP/M006670/1
• 负责人: Martin Wills
• 金额: $ 44.22万
• 依托单位: University of Warwick
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2014
• 资助国家: 英国
• 起止时间: 2014 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FM006670%2F1
• 关键词: Asymmetric; Catalysis; Using; Novel; Iron

There is a continual and ongoing requirement to prepare new and more complex molecules, for example as pharmaceutical candidates, agrochemical products and novel materials. In addition, pressures on dwindling resources and energy supplies make it imperative for more efficient routes to be found to known molecules. To achieve these objectives in a sustainable manner, it is necessary to continue to develop more selective and efficient catalysts. These will reduce waste and side-product formation, and have lower energy requirements during use and for subsequent product isolation. This proposal is concerned with the development and evaluation of a series of catalysts for the precise control of the way in which hydrogen atoms are added to specific bonds within a molecule during certain transformations. This process is often an important component of the synthetic approaches to a large proportion of pharmaceutical products and intermediates, agrochemicals and materials. This transformation can often be achieved efficiently using existing catalysts however a drawback of these catalysts is that they are all based on expensive metals, most typically rhodium, ruthenium, iridium and palladium. In addition, the long term security of these very expensive metals is by no means secure and each of them exhibit significant toxicity. For these reasons, there is an increasingly compelling need to reduce the use of precious-metal catalysts in industrial use and to ideally eliminate them fully. In order to address this challenge, this project will focus on the development of catalysts based upon complexes of the transition metal iron, which is known to be a very active for the control of hydrogen addition reactions. Some preliminary related results have already been obtained, which confirm that the proposed synthetic approach to the catalysts is a valid one. The applicant is now set to prepare further extended iron complex derivatives and to test them in hydrogenation reactions. The project will involve the preparation of a broad range of iron-based catalysts with a diverse structure, and these will be tested extensively against a wide range of substrates. Through this process, we shall determine what structural features are most valuable, and which should be avoided. In addition a range of valuable, pharmaceutically-active target molecules will be prepared in order to demonstrate the value of the catalysts.In summary, this project will result in the development of a new class of environmentally friendly, inexpensive and selective catalysts for hydrogen addition to a broad range of substrate classes, thus significantly extending the synthetic power and value of this already pivotal synthetic transformation.

制备新的和更复杂的分子，例如作为药物候选物、农业化学产品和新材料，存在持续和持续的需求。此外，日益减少的资源和能源供应的压力使得找到已知分子的更有效途径成为当务之急。为了以可持续的方式实现这些目标，有必要继续开发更具选择性和高效的催化剂。这将减少废物和副产物的形成，并且在使用期间和随后的产物分离中具有较低的能量需求。该提案涉及开发和评估一系列催化剂，用于精确控制在某些转化过程中氢原子加入分子内特定键的方式。该工艺通常是大部分医药产品和中间体、农用化学品和材料合成方法的重要组成部分。这种转化通常可以使用现有的催化剂有效地实现，然而这些催化剂的缺点是它们都基于昂贵的金属，最典型的是铑、钌、铱和钯。此外，这些非常昂贵的金属的长期安全性绝不是安全的，它们中的每一种都表现出显著的毒性。出于这些原因，越来越迫切地需要减少工业用途中贵金属催化剂的使用，并理想地完全消除它们。为了应对这一挑战，该项目将专注于开发基于过渡金属铁络合物的催化剂，众所周知，过渡金属铁对于控制氢加成反应非常活跃。已经获得了一些初步的相关结果，这证实了所提出的催化剂合成方法是有效的。申请人现在准备制备进一步延伸的铁络合物衍生物并在氢化反应中测试它们。该项目将涉及制备一系列具有不同结构的铁基催化剂，并将针对各种基质进行广泛测试。通过这个过程，我们将确定哪些结构特征最有价值，哪些应该避免。此外，还将制备一系列有价值的、具有药物活性的目标分子，以证明催化剂的价值。总之，该项目将导致开发出一类新的环境友好、廉价和选择性的催化剂，用于氢加成到广泛的底物类别，从而显着扩展这一已经至关重要的合成转化的合成能力和价值。

项目成果

Asymmetric ruthenium tricarbonyl cyclopentadienone complexes; synthesis and application to asymmetric hydrogenation of ketones

不对称钌三羰基环戊二烯酮配合物；

• DOI: 10.1016/j.ica.2019.119043
• 发表时间: 2019
• 期刊: Inorganica Chimica Acta
• 影响因子: 2.8
• 作者: Del Grosso A

Increasing the versatility of the biphenyl-fused-dioxacyclodecyne class of strained alkynes.

• DOI: 10.1039/d3ob01712e
• 发表时间: 2024-01-17
• 期刊: ORGANIC & BIOMOLECULAR CHEMISTRY
• 影响因子: 3.2
• 作者: Forshaw, Sam;Parker, Jeremy S.;Scott, William T.;Knighton, Richard C.;Tiwari, Neelam;Oladeji, Samson M.;Stevens, Andrew C.;Chew, Yean Ming;Reber, Jami;Clarkson, Guy J.;Balasubramanian, Mohan K.;Wills, Martin
• 通讯作者: Wills, Martin