AsymFeCH · Development and mechanistic investigations of efficient Fe-catalysed asymmetric C–H activation
Horizon 2020 — Marie Skłodowska-Curie Actions
- Duration
- 2020-10-01 → 2022-09-30
- EU contribution
- €162,806
- Participants
- 1
- Scheme
- MSCA-IF
Lines connect the coordinator with its partners.
Results in brief
Development and mechanistic investigations of efficient Fe-catalysed asymmetric C–H activation
In an age where the world is experiencing extraordinary population growth, the demand for goods and services necessary to maintain a high quality of life is higher than ever. To address this need, the concept of sustainability was introduced which encompasses economic development, social development, and environmental protection. Consequently, there is a high demand for developing sustainable technologies which will allow the production of goods not only at a low cost (economic development) but also in a fashion that protects human health (social development) and does not harm the environment (environmental protection). At the same time, the development of metal-mediated catalysis has revolutionized the chemicals manufacturing industry enabling access to a plethora of products that increase life quality and expectancy (pharmaceuticals, pesticides, detergents, synthetic materials, etc.). However, current technologies rely on the use of precious and toxic metals with the concurrent generation of large amounts of waste and therefore are not sustainable. The asymmetric iron-catalyzed C–H activation project (AsymFeCH) was developed to cover the need for highly sustainable catalytic systems by combining the versatility and ability of C–H activation to access useful organic products in fewer steps (byproduct reduction), using inexpensive, non-toxic, and abundant iron-based catalysts. In addition, understanding how the developed systems operate through detailed mechanistic investigations opens the path for the development of asymmetric reactions where only one of the two enantiomeric products is obtained further increasing the sustainability of the overall process. Therefore, the AsymFeCH project contributes to the development of sustainable technologies that aim towards making products accessible to everyone in society and reducing the impact that their production has on the environment and human health. Consequently, the objective of this Marie Skłodowska Curie Action (MSCA) is to first understand the way iron-catalyzed C–H activation reactions operate through detailed mechanistic investigations. Subsequently, the obtained knowledge can be used for the development of environmentally benign, sustainable reactions and ultimately for developing challenging enantioselective systems. At the same time, the skill of the researcher is further developed enabling him in that way to further contribute to the current socioeconomic needs through his research in the field. These objectives were achieved by understanding the mechanism by which low valent iron-catalyzed systems operate which in turn led to the development of novel highly sustainable iron-photocatalyzed C–H activations.
Data: CORDIS, © European Union
Project objective
The importance of chirality in bioactive molecules is well established with only one enantiomer exhibiting the desired biological activity. To date, more than 90% of chiral drugs on the market are supplied as racemates potentially causing side-effects or of uncertain bioactivity. The enantioselective synthesis of chemicals has risen to address such issues with enantioselective catalytic C–H activation standing out due to its atom economy, step efficiency, and avoidance of substrate pre-functionalization. So far, metal-catalysed enantioselective inner sphere C–H activation relies mainly on precious and/or toxic metals, such as Pd and Ru, limiting the reaction’s applicability. Therefore, efforts are currently being made to replace such metals with more benign 3rd row transition metals. Nevertheless, only one report of such transformation has been reported with Fe despite Fe being extremely desirable due to its low cost, toxicity and high natural abundance. The AsymFeCH project will address this issue through the development of non-toxic, sustainable and inexpensive Fe-catalysed enantioselective C–H activation reactions. For this purpose, low valent Fe complexes with chiral phosphines will be used as precatalysts in the catalytic hydroarylation of allenes or alkenes with aromatic ketones. The mechanism and origin of enantioselectivity of the developed reactions will then be delineated through a unique combination of spectroscopies and kinetic studies. Subsequently, the acquired mechanistic understanding will be used for further reaction development with more challenging substrates (imines and 1,1-diphenylketone derivatives) setting the foundations for the scientific and industrial communities to advance the field of asymmetric Fe-catalysed C-H activation. This will not only lead to the sustainable and greener synthesis of pure chiral products affecting the pharmaceutical and materials sectors but will also make Europe less dependent on Pd, an imported precious metal.
Original text from CORDIS.
Participants
- GEORG-AUGUST-UNIVERSITAT GOTTINGEN STIFTUNG OFFENTLICHEN RECHTS · GottingenCoordinatorGermany
Links
Data: CORDIS, © European Union