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Acoplamiento conjuntivo enantioselectivo catalizado por Ni con C ((sp³) Electrófilos: una dicotomía mecanicista

Gabriel J Lovinger¹, James P Morken¹

¹Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.

Journal of the American Chemical Society

|November 9, 2017

Resumen

La catálisis del níquel permite el acoplamiento enantioselectivo de electrófilos C ((sp3). Los resultados de la reacción varían según la estructura y el mecanismo del sustrato, lo que influye en el éxito de la síntesis asimétrica con complejos Pybox-Ni.

Área de la Ciencia:

Química orgánica
Catálisis
Síntesis asimétrica

Sus antecedentes:

Los electrófilos C ((sp3) son bloques de construcción cruciales en la síntesis orgánica.
El logro del acoplamiento enantioselectivo de los centros de C ((sp3) sigue siendo un desafío importante.
La catálisis del níquel ofrece una vía prometedora para la funcionalización del C ((sp3).

Objetivo del estudio:

Investigar el acoplamiento conjuntivo enantioselectivo catalítico de electrófilos C ((sp3) utilizando la catálisis del níquel (Ni).
Comprender la influencia de los mecanismos de reacción en la enantioselectividad.
Establecer la relación entre la estructura del sustrato y la selectividad de la reacción de acoplamiento.

Principales métodos:

El uso de complejos Pybox-Ni como catalizadores para la reacción de acoplamiento conjuntivo.
Variación sistemática de las estructuras de sustrato para sondear las relaciones estructura-selectividad.
Análisis de los mecanismos de reacción para determinar los factores que rigen la enantioselectividad.

Principales resultados:

Se ha demostrado el éxito del acoplamiento conjuntivo enantioselectivo catalítico de electrófilos C ((sp3) con catálisis de Ni.
Se identificó que la enantioselectividad es críticamente dependiente del mecanismo de reacción.
Se observó que ciertos sustratos producen productos enriquecidos enantioméricamente con complejos Pybox-Ni, mientras que otros producen mezclas racémicas.

Conclusiones:

La catálisis del níquel es eficaz para el acoplamiento conjuntivo enantioselectivo de electrófilos C ((sp3).
La interacción entre la estructura del sustrato y el mecanismo de reacción dicta el éxito de la inducción asimétrica.
Para una aplicación más amplia de esta metodología, se justifica una mayor investigación de los mecanismos controlados por el sustrato.

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