Visible light-driven dearomative meta-cycloadditions of 2-acetonaphthalenes via triplet energy transfer cascade
Abstract Dearomative cycloadditions (DACs) with ortho- and para-variants have been well documented under visible light-mediated triplet-triplet energy transfer (VLEnT) catalysis. The prospective [3 + 2] or the meta-DACs propelled via VLEnT catalysis remains elusive. Classically, meta-DACs are known...
Saved in:
| Main Authors: | , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-03-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-58285-5 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1849392520771928064 |
|---|---|
| author | Pramod Rai Sanghamitra Naik Kriti Gupta Kakoli Maji Garima Jindal Biplab Maji |
| author_facet | Pramod Rai Sanghamitra Naik Kriti Gupta Kakoli Maji Garima Jindal Biplab Maji |
| author_sort | Pramod Rai |
| collection | DOAJ |
| description | Abstract Dearomative cycloadditions (DACs) with ortho- and para-variants have been well documented under visible light-mediated triplet-triplet energy transfer (VLEnT) catalysis. The prospective [3 + 2] or the meta-DACs propelled via VLEnT catalysis remains elusive. Classically, meta-DACs are known under harsher UV irradiations and are symmetry allowed in the excited singlet potential energy surface. Herein, we report formal meta-DACs of 2-acetonaphthalenes propagated via a two-step VLEnT cascade circumventing the attainment of energetically higher singlet excited states. The photosensitizer selectively promotes the [4 + 2] cycloaddition followed by a contra-thermodynamic di-π-methane type skeleton rearrangement cascade. The DFT studies in conjugation with electrochemical, photoluminescence, kinetic, quadratic dependency, and control experiments support the VLEnT cascade. The described protocol delivers highly sp3-rich polycyclic frameworks in high yields with wide functional group tolerance. The inclusion of bioactive molecules and the establishment of a wide array of post-synthetic derivatizations further underscores the adaptability of the methodology for generating complex three-dimensional molecules. |
| format | Article |
| id | doaj-art-05522cb8fa7c4312a046cc828816665d |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-05522cb8fa7c4312a046cc828816665d2025-08-20T03:40:45ZengNature PortfolioNature Communications2041-17232025-03-0116111310.1038/s41467-025-58285-5Visible light-driven dearomative meta-cycloadditions of 2-acetonaphthalenes via triplet energy transfer cascadePramod Rai0Sanghamitra Naik1Kriti Gupta2Kakoli Maji3Garima Jindal4Biplab Maji5Department of Chemical Sciences, Indian Institute of Science Education and Research KolkataDepartment of Chemical Sciences, Indian Institute of Science Education and Research KolkataDepartment of Organic Chemistry, Chemical Sciences Division, Indian Institute of ScienceDepartment of Chemical Sciences, Indian Institute of Science Education and Research KolkataDepartment of Organic Chemistry, Chemical Sciences Division, Indian Institute of ScienceDepartment of Chemical Sciences, Indian Institute of Science Education and Research KolkataAbstract Dearomative cycloadditions (DACs) with ortho- and para-variants have been well documented under visible light-mediated triplet-triplet energy transfer (VLEnT) catalysis. The prospective [3 + 2] or the meta-DACs propelled via VLEnT catalysis remains elusive. Classically, meta-DACs are known under harsher UV irradiations and are symmetry allowed in the excited singlet potential energy surface. Herein, we report formal meta-DACs of 2-acetonaphthalenes propagated via a two-step VLEnT cascade circumventing the attainment of energetically higher singlet excited states. The photosensitizer selectively promotes the [4 + 2] cycloaddition followed by a contra-thermodynamic di-π-methane type skeleton rearrangement cascade. The DFT studies in conjugation with electrochemical, photoluminescence, kinetic, quadratic dependency, and control experiments support the VLEnT cascade. The described protocol delivers highly sp3-rich polycyclic frameworks in high yields with wide functional group tolerance. The inclusion of bioactive molecules and the establishment of a wide array of post-synthetic derivatizations further underscores the adaptability of the methodology for generating complex three-dimensional molecules.https://doi.org/10.1038/s41467-025-58285-5 |
| spellingShingle | Pramod Rai Sanghamitra Naik Kriti Gupta Kakoli Maji Garima Jindal Biplab Maji Visible light-driven dearomative meta-cycloadditions of 2-acetonaphthalenes via triplet energy transfer cascade Nature Communications |
| title | Visible light-driven dearomative meta-cycloadditions of 2-acetonaphthalenes via triplet energy transfer cascade |
| title_full | Visible light-driven dearomative meta-cycloadditions of 2-acetonaphthalenes via triplet energy transfer cascade |
| title_fullStr | Visible light-driven dearomative meta-cycloadditions of 2-acetonaphthalenes via triplet energy transfer cascade |
| title_full_unstemmed | Visible light-driven dearomative meta-cycloadditions of 2-acetonaphthalenes via triplet energy transfer cascade |
| title_short | Visible light-driven dearomative meta-cycloadditions of 2-acetonaphthalenes via triplet energy transfer cascade |
| title_sort | visible light driven dearomative meta cycloadditions of 2 acetonaphthalenes via triplet energy transfer cascade |
| url | https://doi.org/10.1038/s41467-025-58285-5 |
| work_keys_str_mv | AT pramodrai visiblelightdrivendearomativemetacycloadditionsof2acetonaphthalenesviatripletenergytransfercascade AT sanghamitranaik visiblelightdrivendearomativemetacycloadditionsof2acetonaphthalenesviatripletenergytransfercascade AT kritigupta visiblelightdrivendearomativemetacycloadditionsof2acetonaphthalenesviatripletenergytransfercascade AT kakolimaji visiblelightdrivendearomativemetacycloadditionsof2acetonaphthalenesviatripletenergytransfercascade AT garimajindal visiblelightdrivendearomativemetacycloadditionsof2acetonaphthalenesviatripletenergytransfercascade AT biplabmaji visiblelightdrivendearomativemetacycloadditionsof2acetonaphthalenesviatripletenergytransfercascade |