HaloCat · Elemental Halogen-Free Reversible Construction and Deconstruction of 1,2-Dihalides via Shuttle Catalysis
Horizon 2020 — Marie Skłodowska-Curie Actions
- Duration
- 2020-06-01 → 2022-05-31
- EU contribution
- €203,149
- Participants
- 1
- Scheme
- MSCA-IF-EF-ST
Lines connect the coordinator with its partners.
Results in brief
Elemental Halogen-Free Reversible Construction and Deconstruction of 1,2-Dihalides via Shuttle Catalysis
Polyhalides are essential commodity chemicals and indispensable synthetic intermediates, while their synthesis has heavily relied on the use of elemental chlorine and bromine. However, Cl2 and Br2 are infamous for their highly toxic and corrosive properties. Thousands of reported chemical accidents during the production, transport, storage, and handling of Cl2 and Br2 call for alternative and safer approaches to alleviate their usage. Meanwhile, several previously widely used halogenated commodity chemicals, such as Lindane [gamma-hexachloro-cyclohexane (HCH)], have been classified as persistent organic pollutants (POPs) and banned from use, due to their environmental persistence and devastating effects on humans and the environment. The valorization of end-of-life halogenated products has been a long sought-after goal in sustainable chemistry. This MSCA project, HaloCat, aims to develop a practical and sustainable approach to reversibly shuttle the corrosive and toxic entities (e.g. Cl2, Br2, RSCl and RSBr) between two molecules. On the one hand, it will alleviate the use of corrosive and toxic elemental chlorine and bromine in synthesis, enhancing the safety of chemical processes. On the other hand, it will provide a sustainable way to recycle persistent organic pollutants (POPs), contributing to a sustainable future.
Data: CORDIS, © European Union
Project objective
Multi-halogenated compounds play a significant role in our daily life, as they are not only widely used as materials, pharmaceuticals, and agrochemicals but also serve as practical and indispensable building blocks in the chemical industry. However, most of the existing halogenating protocols suffer from safety risks and harsh reaction conditions caused by toxic and corrosive halogenating reagents (Cl2, Br2). Moreover, the enantioselective 1,2-dihalogenation of alkenes remains an unmet challenge. Besides, practical approaches to the versatile 1,2-bromofluorine-containing building blocks are exceedingly rare. Recently, the shuttle catalysis strategy, which reversibly transfers a chemical moiety between two molecules to construct and deconstruct compounds without handling hazardous reagents, is emerging as a potential strategy to tackle these long-standing challenges. This proposal aims to achieve the shuttle catalysis enabled reversible interconversion of 1,2-dihalides and alkenes/alkynes without using or releasing hazardous chemicals (e.g., Br2, Cl2, and BrF) under mild conditions. The first part is devoted to developing the reversible interconversion between 1,2-dihalides and alkenes. The second part aims to realize the enantioselective Br2 transfer between 1,2-dihalides and alkenes. The last part proposes to develop the unprecedented formal transfer 1,2-bromofluorination of alkenes via a unique self-correcting mechanism. The world-leading research environment of ETH Zurich combined with Prof. Morandi’s unrivaled scientific expertise on shuttle catalysis and my excellent knowledge of asymmetric catalysis offer the best combination to achieve the proposed research. This fellowship will dramatically improve my knowledge and competences, helping me launch my independent career. With promising preliminary results demonstrating the project’s feasibility, the proposed work will significantly contribute to the research excellence and sustainable development of the EU.
Original text from CORDIS.
Participants
- EIDGENOESSISCHE TECHNISCHE HOCHSCHULE ZUERICH · ZuerichCoordinatorSwitzerland
Links
Data: CORDIS, © European Union