Redox-neutral photocatalytic hydrodealkenylation of aryl olefins
Abstract Carbon-carbon bond cleavage is a transformative strategy in chemical synthesis, particularly for modifying complex molecules. While the cleavage of C(sp²)=C(sp²) π-bonds is relatively straightforward, the selective cleavage of unpolarized C(sp²)–C(sp³) σ-bonds remains a significant challeng...
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| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-60229-y |
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| Summary: | Abstract Carbon-carbon bond cleavage is a transformative strategy in chemical synthesis, particularly for modifying complex molecules. While the cleavage of C(sp²)=C(sp²) π-bonds is relatively straightforward, the selective cleavage of unpolarized C(sp²)–C(sp³) σ-bonds remains a significant challenge. In this study, we present a redox-neutral approach for hydrodealkenylation, enabling the selective cleavage of C(sp²)–C(sp³) σ-bonds in aryl olefins. This reaction proceeds via a cascade of aryl radical cation-mediated open-shell steps under photoredox conditions, incorporating an alkene migration step that exhibits high selectivity and synthetic versatility. This protocol facilitates the selective removal of a vinyl group from arylalkene substrates, yielding isolable fragments. Moreover, this method extends beyond single-bond cleavage by enabling a domino reaction sequence capable of cleaving multiple inert carbon-carbon σ-bonds and allowing programmable chain homologation. This work advances the field of σ-bond cleavage and functionalization, offering a versatile tool for the molecular editing of hydrocarbons with significant implications for synthetic chemistry and the development of novel chemical transformations. |
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| ISSN: | 2041-1723 |