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Hidroaminación remota de alquenos disubstituidos mediante una combinación de isomerización y adición regioselectiva

Senjie Ma^1,2, Haoyu Fan¹, Craig S Day¹

¹Department of Chemistry, University of California, Berkeley, California 94720, United States.

Journal of the American Chemical Society

|February 13, 2023

Resumen

Este estudio introduce un nuevo método para la hidroaminación remota, añadiendo selectivamente grupos funcionales a posiciones no activadas en alquenos. Este avance permite la síntesis regioselectiva de aminas a partir de isómeros de alqueno mezclados.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

Las hidrofuncionalizaciones remotas introducen grupos funcionales lejos de los enlaces dobles de alqueno existentes.
Los métodos existentes involucran principalmente enlaces no polares B-H, Si-H y C-H, con carbonilaciones remotas bien establecidas.
La funcionalización selectiva de las cadenas alquilo no activadas sigue siendo un desafío significativo en la síntesis orgánica.

Objetivo del estudio:

Desarrollar un nuevo sistema para la hidroaminación remota de alquenos disubstituidos.
Para lograr la funcionalización selectiva en la posición de metileno no activado subterminal de las cadenas alquilo.
Para permitir la síntesis regioselectiva de aminas a partir de mezclas de alquenos isoméricos.

Principales métodos:

Desarrollo de un sistema catalítico para la hidroaminación remota.
Optimización de las propiedades electrónicas y estéricas del ligando, incluido el nuevo ligando DIP-Ad-SEGPHOS.
Evaluación de los efectos de los sustituyentes sobre la reactividad de las aminas y la selectividad de las reacciones.

Principales resultados:

Exitosa hidroaminación remota de alquenos disueltos con alta regioselectividad en la posición de metileno no activado.
Demostración de la compatibilidad con una amplia gama de alquenos y aminopiridinas.
Síntesis regioconvergente de aminas a partir de mezclas de isómeros de alqueno.

Conclusiones:

El sistema desarrollado proporciona una nueva herramienta poderosa para la funcionalización selectiva de C-H a través de la hidroaminación remota.
El diseño del ligando (DIP-Ad-SEGPHOS) es crucial para lograr una alta reactividad y selectividad.
Los productos de amina sintetizados pueden modificarse aún más mediante la sustitución aromática nucleofílica.

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