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Intercambio de haluros catalizados sin oxidantes y reacciones formadoras de enlaces C

Jordi Serra¹, Christopher J Whiteoak¹, Ferran Acuña-Parés¹

¹Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona , Campus de Montilivi, Girona E-17071, Catalonia, Spain.

Journal of the American Chemical Society

|September 24, 2015

Resumen

Este estudio introduce nuevas reacciones catalizadas por oro para el intercambio de haluros y la formación de enlaces Csp2-O que no requieren oxidantes externos. Estos hallazgos avanzan en la catálisis del oro al permitir reacciones eficientes de acoplamiento cruzado de heteroátomos de carbono en condiciones más suaves.

Área de la Ciencia:

Química organometálica
Catálisis
Síntesis orgánica

Sus antecedentes:

La catálisis del oro es versátil, utilizando la acidez de Lewis y las propiedades redox.
Las reacciones redox catalizadas por oro tradicionales a menudo requieren oxidantes externos fuertes debido al alto potencial de oxidación de la pareja Au (I) / Au (III).

Objetivo del estudio:

Para demostrar el intercambio de haluros catalizados por oro (I) sin oxidantes externos y la formación de enlaces Csp2-O.
Explorar el alcance y el mecanismo de estas nuevas reacciones.

Principales métodos:

Se utilizó un modelo de sustrato macrocíclico de haluro de arilo para reacciones catalizadas por oro.
Se ha investigado la reactividad con sustratos que contienen un solo grupo quelante.
Reacciones de intercambio de haluros realizadas, incluida la fluoración.
Se ha examinado la formación de enlaces Csp2-O (eterificación).

Principales resultados:

Se ha logrado un intercambio de haluros catalizados por Au (I) sin oxidantes externos, incluida la fluoración.
Se ha demostrado la formación de enlaces Csp2-O catalizados por Au ((I) sin oxidantes externos.
Reactividad extendida a sustratos con un solo grupo quelante.
Se establecieron los primeros ejemplos de acoplamiento cruzado de heteroátomos de carbono catalizados por Au (I) sin oxidantes externos.

Conclusiones:

Desarrollo de nuevos métodos catalizados por oro para el intercambio de haluros y la formación de enlaces Csp2-O sin oxidantes externos.
Proporcionó información mecanicista sobre estas reacciones a través de la expansión del alcance del sustrato.
Preparó el camino para reacciones de acoplamiento cruzado catalizadas por oro más sostenibles y eficientes.

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