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Resolución cinética dinámica no enzimática de los alcoholes secundarios a través de la acilación enantioselectiva:

Sarah Yunmi Lee¹, Jaclyn M Murphy, Atsushi Ukai

¹Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.

Journal of the American Chemical Society

|September 1, 2012

Resumen

Este estudio presenta la primera resolución cinética dinámica no enzimática de los alcoholes secundarios a través de la acilación enantioselectiva. Un nuevo método de carbonato de acilo supera la incompatibilidad del catalizador, lo que permite una síntesis eficiente de alcoholes quirales.

Área de la Ciencia:

Química orgánica es la química orgánica.
Síntesis asimétrica de síntesis.

Sus antecedentes:

Las subunidades secundarias de carbinol son frecuentes en productos farmacéuticos y productos naturales.
El desarrollo de métodos eficientes de síntesis enantioselectiva para estos compuestos es crucial.

Objetivo del estudio:

Establecer la primera resolución cinética dinámica no enzimática (DKR) de los alcoholes secundarios.
Ampliar el alcance de la acilación enantioselectiva para los alquilcarbinolos de arilo.

Principales métodos:

Desarrolló un método de DKR no enzimático utilizando acilación enantioselectiva.
Evitó la desactivación del catalizador empleando carbonatos de acilo en lugar de anhídrido acético.
Mecanismos de reacción investigados que incluyen el catalizador N-acilación y transferencia de acilo.

Principales resultados:

Se logró DKR de alcoholes secundarios sin catálisis enzimática.
Se identificaron carbonatos de acilo como agentes aciladores compatibles, evitando la desactivación del catalizador de rutenio.
Se aclararon los pasos mecánicos clave, incluida la transferencia de acilo que determina la velocidad.

Conclusiones:

El método DKR no enzimático desarrollado ofrece una valiosa alternativa a los enfoques enzimáticos.
El uso de carbonatos de acilo es crítico para una resolución cinética dinámica exitosa con catalizadores de rutenio.
Las ideas mecánicas guían una mayor optimización de los procesos de acilación enantioselectiva.

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