TransNic · Enantioselective Nickel-Catalyzed trans-Carbometallative Couplings and Cyclizations
Horizon 2020 — Marie Skłodowska-Curie Actions
- Duration
- 2016-08-01 → 2018-07-31
- EU contribution
- €195,455
- Participants
- 1
- Scheme
- MSCA-IF-EF-ST
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Results in brief
Enantioselective Nickel-Catalyzed trans-Carbometallative Couplings and Cyclizations
"""Alkenylmetal species"" are versatile synthetic intermediates in chemistry, which, in their simplest form, are composed of a metal atom bonded to a two-carbon fragment. Alkenylmetal species are used in a wide range of reactions to produce numerous important chemical building blocks. In the Host Laboratory, a new method to access alkenylmetal species resulting from formal anti-carbometallation was discovered. This process involves an initial syn-addition to a carbon-carbon triple bond to give an alkenylmetal species that then undergoes reversible E/Z isomerization to the anti-product which is responsible for further functionalization. In the original discovery, nickel was used as the metal, and the resulting alkenylnickel species was used to react with another group in the same molecule to form a cyclic compound. The key feature about this reversible E/Z isomerization reaction is that it enables reactions to proceed that would otherwise be impossible on the basis of geometric constraints. The original objectives of this project were to: (a) Define the scope and limitations of this method in producing a wide range of cyclic compounds. (b) Develop variants of these reactions that are able to give products selectively as a single enantiomer (which is defined as a non-superimposable mirror-image form). The ability to produce compounds as single enantiomers is very important because the exact function of compounds within biological systems (e.g. if the compounds are to be used as medicines) often depends upon which mirror image they exist in. The work in this project was highly successful, which led us to further develop and expand the chemistry in the same area. These new methods were successful in producing a wide range of cyclic products in good yields under mild reaction conditions, and at the time of writing, this research has been published in two articles in a leading general chemistry journal. The remaining work is being currently being prepared for publication (Scheme 1–3). "
Data: CORDIS, © European Union
Project objective
This Fellowship application unites an Experienced Researcher from India (but currently based in Taiwan) with expertise in asymmetric synthesis and transition metal catalysis using gold, silver, and rhodium complexes, with an internationally recognized Host Laboratory in the UK with expertise in the development of new catalytic reactions for organic synthesis. This project will:• Provide high-quality, structured training for an outstanding scientist with an excellent publication record who is destined for an independent research career, by complementing and enhancing his competencies.• Showcase European excellence in homogeneous catalysis and organic synthesis, which are critically important branches of chemistry that underpin many sectors, such as the pharmaceutical, fine chemicals, agrochemical, materials, and biochemical industries.The proposed research is based upon a new synthetic method recently discovered in the Host Laboratory that relies upon the formal trans-carbometallation of organonickel species across an alkyne. The resulting alkenylnickel species can be trapped by various electrophiles in cyclizations that would otherwise be impossible, giving densely functionalized carbo- and heterocyclic scaffolds. Moreover, the products can be obtained with high enantioselectivities using a chiral ligand. We believe this chemistry carries enormous potential, and the final result will be a powerful synthetic method for the preparation of valuable building blocks as single enantiomers. This Fellowship will therefore help Europe to remain globally competitive in the chemical sciences.
Original text from CORDIS.
Participants
- THE UNIVERSITY OF NOTTINGHAM · NottinghamCoordinatorUnited Kingdom
Links
Data: CORDIS, © European Union