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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Síntesis y reactividad de los azapalladaciclobutanos
1Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109-1055, USA.
Journal of the American Chemical Society
|November 30, 2006
Resumen
Las N-sulfonil aziridinas reaccionan con el paladio para formar nuevos complejos bicíclicos. Estos compuestos pueden ser funcionalizados aún más, ofreciendo nuevas vías en la química organometálica.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- Química orgánica sintética y orgánica.
Sus antecedentes:
- La catálisis del paladio es crucial para la formación de enlaces C-C y C-heteroatomo.
- Las aziridinas son versátiles heterociclos de tres miembros utilizados en la síntesis orgánica.
Objetivo del estudio:
- Para investigar la reactividad de las N-sulfonil aziridinas con los complejos de paladio.
- Explorar la formación de nuevos intermediarios de organopalladio y sus posteriores transformaciones.
Principales métodos:
- La generación in situ de complejos de paladio (((0) utilizando Pd2 (((dba) 3 y 1,10-fenantrolina.
- La adición oxidativa de las N-sulfonil aziridinas al paladio(0).
- La carbopaladación intramolecular es facilitada por el cobre (I) yoduro.
- Estudios de etiquetado de deuterio para elucidar los mecanismos de reacción.
- Funcionalización oxidativa de los enlaces C-Pd mediante el uso de bromuro de cobre.
Principales resultados:
- Las N-sulfonil aziridinas se someten a una adición oxidativa al paladio para producir azapalladaciclobutanos intermedios.
- La carbopaladación intramolecular de estos intermediarios conduce a la formación de azapalladabiciclo[3.2.1]octanes.
- El etiquetado de deuterio confirmó el ataque de tipo SN2 en la inserción de carbono de aziridina y alqueno de sin-moda menos obstaculizada.
- Los complejos bicíclicos son susceptibles a una mayor funcionalización a través de la química de enlaces oxidativo paladio-carbono.
Conclusiones:
- Se ha establecido una nueva vía sintética para los azapalladabiciclo[3.2.1]octanos de las N-sulfonil aziridinas.
- El estudio proporciona información mecanicista sobre la reacción catalizada por el paladio, incluidos los resultados estereoquímicos.
- La metodología desarrollada ofrece potencial para la construcción de arquitecturas moleculares complejas.
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