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Enfoques deconstructivos mediados por la foto y el metal para la diversificación de aminas alifáticas cíclicas

David M Soro¹, Jose B Roque¹, Jonas W Rackl¹

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

Journal of the American Chemical Society

|May 12, 2023

Resumen

Este estudio detalla nuevos métodos para modificar las aminas alifáticas cíclicas. Se lograron nuevas reacciones de apertura de anillos y de interconversión de heterociclos utilizando fotocatálisis o catalizadores metálicos como el cobre y la plata.

Área de la Ciencia:

Química orgánica
Catálisis
La fotoquímica

Sus antecedentes:

Las aminas alifáticas cíclicas son motivos estructurales importantes en la química orgánica.
Los métodos eficientes para su funcionalidad y remodelación estructural son muy buscados.
Los métodos existentes a menudo carecen de selectividad o requieren condiciones duras.

Objetivo del estudio:

Desarrollar nuevos métodos catalíticos para la modificación del núcleo de aminas alifáticas cíclicas.
Para explorar la escisión de enlaces oxidativos C-N y C-C para las reacciones de apertura de anillos.
Demostrar la interconversión de heterociclos a través de vías radicales mediadas por metales.

Principales métodos:

Las reacciones catalizadas por riboflavina/fotorradiación mediante el uso de peroxidisulfato.
Reacciones de apertura de anillos oxidativas mediadas por cobre (I) y plata (I).
Estudios computacionales para elucidar los mecanismos de reacción.

Principales resultados:

Apertura del anillo a aldehídos lineales o ácidos carboxílicos mediante fotocatálisis o sales de Cu.
El acoplamiento descarboxilativo Csp3-Csp2 mediado por Ag{\displaystyle Ag{\text{I}}} a través de radicales alquilo intermedios.
Transformación mediada por Cu (II) de aminas cíclicas N-acilo en oxazinas.

Conclusiones:

Se han desarrollado sistemas catalíticos versátiles para la funcionalización de aminas cíclicas.
Las investigaciones mecanicistas apoyan las vías propuestas que implican radicales intermedios.
Estos métodos ofrecen nuevas vías para sintetizar moléculas complejas que contienen nitrógeno.

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