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APCP_TPB

Axial / Planar Chiral Photosensitizers for asymmetric Thia-Paternò–Büchi reactions
Funder: French National Research Agency (ANR)Project code: ANR-24-CE07-3688
Funder Contribution: 432,384 EUR

APCP_TPB

Description

Thietanes stand out among other sulfur compounds as central scaffolds in many bioactive and natural products. They are also unequivocally recognized as highly valuable intermediates in organic synthesis. However, unlike the [2+2]-photocycloaddition of imines and, especially, carbonyl derivatives, the so-called thia-Paternò-Büchi reaction, which combines a photochemically excited thiocarbonyl compound with an alkene partner to form the thietane core, has received very scant attention and an enantioselective version of this transformation has not yet been reported in the literature. In this context, and based on very promising preliminary results, this collaborative research project APCP_TPB, resulting from a valuable combination of complementary French expertise, aims to develop visible-light promoted enantioselective thia-Paternò-Büchi reactions involving axial and planar chiral photosensitizers. Thanks to judicious designed binaphthyl- and [2.2]paracyclophane-based photocatalysts, this methodology will afford a sustainable synthetic access to a large diversity of highly valuable functionalized enantioenriched thietane derivatives. By combining the asymmetric version of this [2+2]-photocycloaddition with post-functionalization reactions of four-membered heterocycles into various photochemical domino sequences, diverse sulfur-containing heterocycles will be targeted. Finally, the high potential of these prepared chiral binaphthyl- and [2.2]paracyclophane-based catalysts will be demonstrated by their use in other photochemical and thermal innovative asymmetric transformations.

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