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Oxidación aeróbica eficiente y selectiva de alcoholes en aldehídos y cetonas utilizando rutenio/TEMPO como el sistema

A Dijksman¹, A Marino-González, A Mairata I Payeras

¹Laboratory for Organic Chemistry and Catalysis, Department of Biotechnology, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.

Journal of the American Chemical Society

|July 13, 2001

Resumen

Un catalizador de rutenio/TEMPO oxida eficientemente los alcoholes a aldehídos y cetonas utilizando oxígeno. Los estudios mecánicos sugieren una vía hidridométrica, que no involucra intermediarios de oxoretenio u oxoamonio.

Área de la Ciencia:

La catálisis de la catálisis.
Química orgánica es la química orgánica.
Reacciones de oxidación Reacciones de oxidación.

Sus antecedentes:

Los complejos de rutenio y los radicales nitroxilo como TEMPO son catalizadores conocidos.
La oxidación aeróbica de los alcoholes es una transformación fundamental en la síntesis orgánica.

Objetivo del estudio:

Desarrollar un sistema catalítico eficiente para la oxidación del alcohol.
Para aclarar el mecanismo de reacción del sistema Ru/TEMPO.

Principales métodos:

Oxidación aeróbica catalítica de alcoholes primarios y secundarios utilizando RuCl2 y TEMPO.
Estudios cinéticos que incluyen correlaciones de Hammett y mediciones de efectos de isótopos cinéticos primarios.
Investigaciones mecanicistas para diferenciar entre las vías propuestas.

Principales resultados:

El sistema Ru/TEMPO logró una selectividad >99% para la formación de aldehídos y cetonas a partir de varios alcoholes.
El catalizador mostró una preferencia por la oxidación de los alcoholes primarios sobre los secundarios.
Los datos cinéticos (rho = -0.58, kH/kD = 5.1) fueron inconsistentes con los mecanismos de oxorutenio u oxoamonio.

Conclusiones:

Se propone un nuevo mecanismo hidridométrico que involucra una especie "RuH2(PPh3)3" para el ciclo catalítico.
TEMPO funciona como un mediador de transferencia de hidrógeno, regenerado por el oxígeno en condiciones aeróbicas.
Los hallazgos proporcionan nuevos conocimientos mecanicistas sobre las oxidaciones de alcohol aeróbico catalizadas por Ru.

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