Dynamic multiligand catalysis: a polar to radical crossover strategy expands alkyne carboboration to unactivated secondary alkyl halides
We describe a dual strategy in Cu catalysis based on an unprecedented dynamic multiligand coordination pool that triggers cooperative polar/radical pathways in a single catalytic cycle. This strategy has been applied to address a restricting limitation inherent to Cu-catalyzed B2pin2-carboboration o...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2021 |
| País: | España |
| Institución: | Universidad Autónoma de Madrid |
| Repositorio: | Biblos-e Archivo. Repositorio Institucional de la UAM |
| Idioma: | inglés |
| OAI Identifier: | oai:repositorio.uam.es:10486/699380 |
| Acceso en línea: | http://hdl.handle.net/10486/699380 https://dx.doi.org/10.1016/j.chempr.2021.06.002 |
| Access Level: | acceso abierto |
| Palabra clave: | Cu catalysis Alkenyl boronates Alkynes Carboboration Dynamic multiligand catalysis Polar/radical crossover Secondary alkyl halides Tetrasubstituted alkenes Química |
| Sumario: | We describe a dual strategy in Cu catalysis based on an unprecedented dynamic multiligand coordination pool that triggers cooperative polar/radical pathways in a single catalytic cycle. This strategy has been applied to address a restricting limitation inherent to Cu-catalyzed B2pin2-carboboration of alkynes—the very low reactivity of the intermediate vinyl-Cu(I) species, which renders conventional methods ineffective with alkyl electrophiles other than simple primary halides. The crossover strategy enabled by ligand exchange in an organometallic intermediate overcomes this reactivity issue, expanding the scope of carboboration to unactivated secondary alkyl halides, and opens new avenues to access stereodefined tetrasubstituted vinylboronates. The method is regio- and stereoselective, shows excellent functional group tolerance, and allows the incorporation of complex carbo- and heterocyclic fragments at either reaction partner |
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