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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
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Luz visible brillante en la eliminación reductora: acoplamiento cruzado acridina-Pd catalizado de haluros de arilo
Naoyuki Toriumi1, Tomonori Inoue1, Nobuharu Iwasawa1
1Department of Chemistry, Tokyo Institute of Technology, O̅okayama, Meguro-ku, Tokyo 152-8551, Japan.
Journal of the American Chemical Society
|October 11, 2022
Resumen
Los nuevos ligandos de fosfinoacridina permiten reacciones eficientes de acoplamiento cruzado catalizadas por paladio utilizando luz visible. Este enfoque único de catálisis de metales de transición utiliza la energía de la luz de manera más efectiva para la síntesis orgánica.
Área de la Ciencia:
- Química orgánica
- La fotoquímica
- Catálisis
Sus antecedentes:
- La catálisis de un solo metal de transición inducida por luz visible está subdesarrollada en comparación con la catálisis dual.
- La utilización eficiente de la energía luminosa en la catálisis sigue siendo un desafío clave en la síntesis orgánica.
Objetivo del estudio:
- Diseñar nuevos ligandos fotosensibilizantes para la catálisis de metales de transición inducida por luz visible.
- Para lograr reacciones de acoplamiento cruzado catalizadas por paladio utilizando haluros de arilo y ácidos carboxílicos bajo luz visible.
Principales métodos:
- Diseño y síntesis de ligandos fotosensibilizantes de la fosfinoacridina bidentada.
- Reacciones de acoplamiento cruzado catalizadas por paladio bajo irradiación de luz visible (luz azul, verde y roja).
- Estudios mecánicos experimentales y cálculos teóricos.
Principales resultados:
- Acoplamiento cruzado exitoso catalizado por paladio de haluros de arilo con ácidos carboxílicos bajo luz visible.
- Catálisis eficaz demostrada con varios haluros de arilo, incluidos los cloruros de arilo menos reactivos.
- Se logró el acoplamiento cruzado utilizando luz azul, verde y roja, lo que indica una amplia aplicabilidad.
- Los estudios mecanicistas confirmaron la eliminación reductiva fotoinducida facilitada por la transferencia de carga de metal a ligando (MLCT).
Conclusiones:
- Los ligandos de fosfinoacridina permiten una catálisis única de metales de transición bajo luz visible.
- La fracción de acridina con deficiencia de electrones promueve la eliminación reductiva fotoinducida a través de MLCT.
- Este trabajo ofrece un raro ejemplo de eliminación reductiva fotoinducida en complejos de paladio, avanzando la catálisis de luz visible.
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