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Enantioselective Photochemical Reactions of Cyclopropene

Objective

In this proposal, we aim to explore the photochemistry of cyclopropene derivatives to access enantioenriched cyclopropenes and polycyclic fused rings with multiple stereocenters. Cyclopropenes can be photochemically excited to form intermediates, depending on the mode of excitation: triplet excitation leads to a diradical intermediate, while singlet excitation leads to a vinyl carbene intermediate. This project is divided into two parts.
In the first part, we will utilize deracemization through selective singlet excitation of cyclopropenes using chiral Lewis acid catalysts. Deracemization converts a racemic mixture into a single enantiomer with 100% efficiency, unlike classical resolution techniques. Cyclic deracemization involves selectively racemizing one enantiomer, leading to the accumulation of the opposite enantiomer. The chiral Lewis acid, coordinated to the ester group of the cyclopropene via two-point binding, will enable selective excitation of one enantiomer into a singlet state. This excited singlet state will collapse into an achiral vinyl carbene, which can cyclize to reform the racemic starting material, driving the mixture toward enantioenriched cyclopropene.
In the second part, we will explore the triplet excitation of cyclopropenes. Triplet excitation activates the olefin rather than the σ-bond, forming a triplet (1,2-diradical) intermediate. We plan to generate this intermediate using a chiral thioxanthone catalyst developed by the Bach group. The chiral environment provided by the catalyst will block one face, allowing selective reaction from one face, leading to enantioenriched bicyclo[2.1.0]pentanes.

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HORIZON-TMA-MSCA-PF-EF - HORIZON TMA MSCA Postdoctoral Fellowships - European Fellowships

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Call for proposal

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(opens in new window) HORIZON-MSCA-2025-PF

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Coordinator

TECHNISCHE UNIVERSITAET MUENCHEN
Net EU contribution

Net EU financial contribution. The sum of money that the participant receives, deducted by the EU contribution to its linked third party. It considers the distribution of the EU financial contribution between direct beneficiaries of the project and other types of participants, like third-party participants.

€ 217 965,12
Address
Arcisstrasse 21
80333 Muenchen
Germany

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Region
Bayern Oberbayern München, Kreisfreie Stadt
Activity type
Higher or Secondary Education Establishments
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Total cost

The total costs incurred by this organisation to participate in the project, including direct and indirect costs. This amount is a subset of the overall project budget.

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