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Enantioconvergente bencílico C ((sp³) -N acoplado con una enzima no hemo sustituida por cobre

Xuzhong Shen¹, Xiahe Chen², Yihang Xiao¹

¹Department of Chemistry, Johns Hopkins University, Baltimore, MD, USA.

Science (New York, N.Y.)

|August 14, 2025

Resumen

Los investigadores desarrollaron un nuevo método fotobiocatalizador para el acoplamiento del radical C ((sp3) -N catalizado por cobre utilizando una enzima modificada. Este avance permite la aminación enantioselectiva, ampliando las aplicaciones de biocatálisis.

Área de la Ciencia:

Química sintética
Biocatálisis
Ingeniería de enzimas

Sus antecedentes:

El acoplamiento de radicales C ((sp3) -N catalizados por cobre es una transformación sintética clave.
Los enfoques enzimáticos para esta reacción han sido limitados.

Objetivo del estudio:

Desarrollar un método enzimático para el acoplamiento de radicales bencílicos C ((sp3) -N.
Para lograr una aminación enantioselectiva utilizando un sistema biocatalítico.

Principales métodos:

Fotobiocatálisis utilizando una enzima no hemo sustituida por cobre (fenilalanina hidroxilasa).
La rodamina B como un catalizador de fotorreducción.
Evolución dirigida para optimizar la actividad enzimática y la selectividad.
Aminación descarboxilada de los ésteres de N-hidroxiftalimida con las anilinas.

Principales resultados:

Implementación exitosa de un sistema fotobiocatalizador para el acoplamiento de radicales bencílicos C ((sp3) -N.
Identificación y ingeniería de una fenilalanina hidroxilasa sustituida por cobre.
Se obtienen altas enantioselectividades para varios sustratos después de la evolución dirigida.
Mecanismo propuesto que involucra un complejo de cobre-anilido que reacciona con un radical bencílico.

Conclusiones:

Este estudio introduce una nueva estrategia fotobiocatalítica para el acoplamiento de radicales catalizados por cobre.
La enzima diseñada facilita la aminación descarboxilada enantioconvergente.
Amplía la utilidad de la catálisis de metales de transición biocatalíticos no naturales.

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