Diboron reagents in N−N bond cleavage of hydrazines, N‐nitrosamines, and azides: Reactivity and mechanistic insights
Diboron reagents are known for their ability to promote the deoxygenation of amine or pyridine oxides, nitroarenes, and nitrones through the formation of B-O-B bonds. In this study, we have investigated the potential of diboron reagents to induce N-N bond cleavage in hydrazines, N-nitrosamines and a...
| Autores: | , , , , |
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| Formato: | artículo |
| Fecha de publicación: | 2025 |
| País: | España |
| Recursos: | Universidad Autónoma de Madrid |
| Repositorio: | Biblos-e Archivo. Repositorio Institucional de la UAM |
| Idioma: | inglés |
| OAI Identifier: | oai:dnet:biblosearchi::d6e9e7c4977bbba5e3c779afab85c6c8 |
| Acesso em linha: | https://hdl.handle.net/10486/777180 https://dx.doi.org/10.1002/chem.202404081 |
| Access Level: | acceso abierto |
| Palavra-chave: | Diboron N-N bond cleavage Hydrazines N-nitrosamines Azides Química |
| Resumo: | Diboron reagents are known for their ability to promote the deoxygenation of amine or pyridine oxides, nitroarenes, and nitrones through the formation of B-O-B bonds. In this study, we have investigated the potential of diboron reagents to induce N-N bond cleavage in hydrazines, N-nitrosamines and azides. Our findings show that the combination of B2nep2 as diboron source and KOMe as a Lewis base can effectively promote the N-N cleavage of a wide variety of substrates. For hydrazines and nitrosamines, the presence of an aryl group is essential for the reaction to proceed, probably due to a better stabilization of the negative charge developed during N-N bond cleavage. Both types of azides, aromatic and aliphatic, are easily reduced, and the resulting amines can be in situ converted into the corresponding amides by simple treatment with a carboxylic acid. Experimental and theoretical calculations suggest a non-radical mechanism, with concerted B-B and N-N bond cleavage in the case of hydrazines and azides, and a stepwise mechanism in the case of N-nitrosamines, where deoxygenation occurs as the first step, involving the formation of an N-nitrene intermediate |
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