Catellani-Inspired BN-Aromatic Expansion: A Versatile Tool toward π-Extended 1,2-Azaborines with Tunable Photosensitizing Properties
BN-isosterism, the replacement of carbon–carbon units with boron–nitrogen pairs in organic frameworks, offers a powerful means to create novel compounds, yet methods to access larger BN-containing polyaromatic cores remain scarce. Leveraging our recently developed multigram-scale synthesis of BN-nap...
| Autores: | , , , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2026 |
| País: | España |
| Institución: | Universitat Ramon Llull (URL) |
| Repositorio: | DAU Arxiu Digital de la Universitat Ramon Llull |
| OAI Identifier: | oai:dau.url.edu:20.500.14342/5968 |
| Acceso en línea: | http://hdl.handle.net/20.500.14342/5968 https://doi.org/10.1021/jacs.5c19389 |
| Access Level: | acceso abierto |
| Palabra clave: | Aromatic compounds Fluorescence Functionalization Hydrocarbons Reaction products Compostos aromàtics Fluorescència Hidrocarburs 54 |
| Sumario: | BN-isosterism, the replacement of carbon–carbon units with boron–nitrogen pairs in organic frameworks, offers a powerful means to create novel compounds, yet methods to access larger BN-containing polyaromatic cores remain scarce. Leveraging our recently developed multigram-scale synthesis of BN-naphthalene, we now combine it with a Catellani-type arene extension (Pd(OAc)2/P(2-furyl)3, norbornene) to rapidly access diverse extended BN-embedded polyaromatic cores. This strategy delivers BN-embedded benzo[c]phenanthridines and curved 8- and 7-membered ring-fused derivatives, as well as BN-embedded benzofluorenones in both normal and inverse BN-vector orientations. Importantly, the ability to access both directional BN isomers, in addition to the parent C═C core, provides a rare opportunity to directly interrogate the effect of the presence and sense of the BN moiety. Most notably, light-induced singlet oxygen (1O2) generation promoted by the benzofluorenone core shows a more than 10-fold enhancement in the “boron-up” BN isostere, while dropping to negligible levels upon inversion of the BN unit. This work thus offers a blueprint for experimental electronic tuning of optically responsive organic materials through BN-mapping. |
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