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Acoplamiento reductor enantioselectivo catalizado por CuH de alquenos de arilo y ácidos carboxílicos activados

Jeffrey S Bandar¹, Erhad Ascic¹, Stephen L Buchwald¹

¹Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.

Journal of the American Chemical Society

|April 29, 2016

Resumen

Un nuevo método catalizado por hidruro de cobre permite el acoplamiento reductor enantioselectivo de alquenos arílicos con derivados de ácido carboxílico. Este enfoque produce cetonas o alcoholes enantioenriquecidos con alta estereoselectividad y amplia tolerancia de grupo funcional.

Área de la Ciencia:

Química orgánica
Catálisis
Síntesis estereoselectiva

Sus antecedentes:

El desarrollo de métodos eficientes para crear moléculas quirales es crucial en la química sintética.
Las reacciones de acoplamiento reductivo son valiosas para la formación de enlaces carbono-carbono.
La catálisis del cobre ofrece una plataforma versátil para diversas transformaciones orgánicas.

Objetivo del estudio:

Introducir un nuevo método de acoplamiento reductor enantioselectivo.
Para explorar los ciclos catalíticos duales que involucran el hidruro de cobre.
Para sintetizar cetonas y alcoholes enantioenriquecidos con α-sustitución.

Principales métodos:

Utilizando la catálisis del hidruro de cobre para el acoplamiento reductivo.
Utilizando como sustratos alquenos de arilo y derivados de ácido carboxílico activado.
Investigación de ciclos catalíticos duales: hidroacilación enantioselectiva seguida de reducción de cetonas diastereoselectiva.

Principales resultados:

Se ha logrado el acoplamiento reductor enantioselectivo de alquenos arilo.
Se han demostrado ciclos catalíticos duales con velocidades distintas.
Cetonas y alcoholes enantioenriquecidos sintetizados con una excelente estereoselectividad.
Se ha demostrado una amplia tolerancia del grupo funcional utilizando anhídridos arilo carboxílicos simétricos.

Conclusiones:

El método desarrollado proporciona una ruta poderosa a las cetonas y alcoholes quirales.
Los ciclos catalíticos duales son clave para la estereoselectividad observada.
La catálisis del hidruro de cobre es eficaz para desafíos sintéticos complejos.

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