NewPropChem · New Frontiers in Propellane Chemistry
Horizon 2020 — Marie Skłodowska-Curie Actions
- Duration
- 2022-02-21 → 2024-02-20
- EU contribution
- €224,934
- Participants
- 1
- Scheme
- MSCA-IF
Lines connect the coordinator with its partners.
Results in brief
New Frontiers in Propellane Chemistry
This MSC Action is titled “New Frontiers in Propellane Chemistry”. This project aims to: (1) develop chemical tools to characterize a ‘landscape’ of propellane reactivity. (2) explore new methods for the catalytic activation of propellane. (3) develop theory-inspired routes to high value [1.1.1]propellanes and derivatives. This work is important because the structures of propellane have fascinated chemists for decades; they are not only found in natural molecules, but also act as a valuable source of rigid cage carbocycles. Propellanes are highly strained, and prone to undergo ring-opening cleavage of the central bond. The smallest propellane is [1.1.1]propellane and ring-opening produce bicyclo[1.1.1]pentane (BCP) which is very much attractive in academia and in industry. Different approaches were tried to synthesize deuterated propellanes and aryl propellanes (WP1). For the synthesis of deuterated propellanes, 4-different routes were tested; out of them strategies A-C were failed, however strategy D worked out (WP1.1). For the synthesis of aryl propellanes, various routes were proposed and investigated, unfortunately all were failed (For the details, see WP1.2). In this project, we mostly spend our time to synthesize deuterated propellanes and aryl propellanes; and were unable to perform another two work packages WP2, and WP3. Overall assessment. The project has achieved some of its objectives and milestones. However, corrective action will be required.
Data: CORDIS, © European Union
Project objective
Propellanes are molecules of high importance as precursors to valuable cage molecules in pharmaceutical and materials research. For smaller-ring propellanes, ubiquitous reactivity can be displayed towards anions, radicals, and cations; however, the theoretical basis for this unusual behaviour has only recently emerged, which is based on the ability of small ring propellanes to delocalise electron density away from the electron-rich central C–C bond onto the peripheral carbon atom p orbitals both in the ground state, and during reactions. In this project we develop chemical tools to test this theoretical model, offering experimental support and characterising the change in structure and electronics during ring opening processes. We further develop new synthetic methodology to access high-value (but hard to access) chiral propellane ring-opening products, and explore new modes of propellane reactivity by employing novel catalytic concepts to activate the central C–C bond. We use a theoretical 'carbene' description of [1.1.1]propellane to open up access to bridge-substituted propellanes, which represent a 'holy grail' of the field, and also explore methods to control the dimerisation or oligomerisation of these molecules. Collectively, using the most up to date theoretical models (and in collaboration with theoretical chemists) we aim to develop a new frontier of propellane chemistry, which has the potential for broad impact on its many applications.
Original text from CORDIS.
Participants
- THE CHANCELLOR, MASTERS AND SCHOLARS OF THE UNIVERSITY OF OXFORD · OxfordCoordinatorUnited Kingdom
Links
Data: CORDIS, © European Union