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Utilizando la ciclización de Bergman mediada por redox hacia el desarrollo de terapias de metalloenediyne de doble
Sarah E Lindahl1, Hyunsoo Park, Maren Pink
1Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.
Journal of the American Chemical Society
|February 26, 2013
Resumen
Un complejo de platino ((0) metaloenediyne estable, Pt ((dppeb) 2), se somete a una eficiente ciclización de Bergman mediada por redox después de la oxidación. Esta reacción produce un subproducto similar al cisplatino, lo que ofrece una nueva estrategia para las terapias de metalloenediyne de doble acción.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- Ciencia de los materiales Ciencia de los materiales.
- Química Medicinal La Química Medicinal es un campo de estudio de la química medicinal.
Sus antecedentes:
- Las metaloenediinas son compuestos que contienen un átomo de metal y una fracción de enediina.
- La ciclización de Bergman es una reacción clave para las enediinas, formando intermedios reactivos parabenzínicos.
- Los complejos de platino se investigan por su potencial terapéutico, especialmente en el tratamiento del cáncer (por ejemplo, cisplatino).
Objetivo del estudio:
- Para sintetizar y caracterizar un complejo de platino (((0) metaloenediyne estable, Pt (((dppeb) 2.2.
- Para investigar la ciclización de Bergman mediada por redox de este complejo.
- Para explorar el potencial de este sistema como una doble amenaza metalloenediyne terapéutica.
Principales métodos:
- Síntesis de Pt (dppeb) 2 a partir de Pt (cod) Cl2 y 1,2-bis (difenilfosfino) etinilbenceno (dppeb).
- Reacciones de oxidación utilizando yodo (I2) con y sin trampas radicales (1,4-ciclohexadieno).
- Caracterización mediante RMN (31P) y espectroscopia Raman.
- Análisis computacional para determinar estructuras plausibles de los intermediarios de reacción.
Principales resultados:
- Se sintetizó el complejo estable Pt(0) Pt(dppeb) 2 y se encontró que era resistente a la oxidación del aire y la ciclización espontánea de Bergman.
- La reacción con I2 y una trampa de radicales produjo rápidamente el producto de diodo ciclizado cis-Bergman.
- La reacción con el exceso de I2 formó un intermediario metastable Pt(dppeb)2(2+) que posteriormente sufrió intercambio de ligandos y ciclización espontánea de Bergman para formar Pt(dppnap-I2)I2.2.
Conclusiones:
- El Pt(0) metalloenediyne Pt(dppeb)2 estable puede activarse de manera eficiente a través de la ciclización de Bergman mediada por redox.
- La reacción produce un subproducto similar al cisplatino, lo que sugiere la posibilidad de una doble acción terapéutica.
- Este sistema representa una nueva estrategia prometedora para el desarrollo de terapias basadas en metalloenediina.
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