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Síntesis de organoborano quiral programado genéticamente

S B Jennifer Kan¹, Xiongyi Huang¹, Yosephine Gumulya¹

¹Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 210-41, Pasadena, California 91125, USA.

|November 30, 2017

Resumen

Los investigadores diseñaron bacterias para crear organoboranas quirales, un nuevo enlace químico que no se encuentra en la naturaleza. Esta plataforma genéticamente codificada permite una biosíntesis eficiente y sintonizable de estos compuestos dentro de las células vivas.

Área de la Ciencia:

Biocatálisis y ingeniería enzimática
Química orgánica sintética
Ingeniería metabólica

Sus antecedentes:

La ingeniería enzimática permite nuevas funciones catalíticas más allá de las capacidades naturales.
La producción celular de enlaces químicos no naturales requiere enzimas y reactivos compatibles.
La creación de organoboranos quirales in vivo presenta desafíos sintéticos significativos.

Objetivo del estudio:

Desarrollar una plataforma bacteriana genéticamente codificada para la producción de organoboranos quirales.
Descubrir y desarrollar variantes de enzimas para la formación eficiente de enlaces carbono-boro.
Para establecer un sistema sintonizable para la manipulación de boro dentro de los organismos vivos.

Principales métodos:

Descubrimiento de la inserción de carbenos en enlaces boro-hidrógeno por el citocromo c de tipo silvestre Rhodothermus marinus (Rma cyt c) en Escherichia coli.
Evolución dirigida de Rma citc para mejorar la actividad y la especificidad para la síntesis de organoborano.
Optimización de la biocatálisis de células enteras para la producción a escala de gramos.

Principales resultados:

Una plataforma para la producción de 16 organoboranos quirales nuevos utilizando Rma cyt c de ingeniería en E. coli.
Eficiencia catalítica alta: hasta 15.300 vueltas, 6.100 h-1, proporción enantiomérica de 99:1 y 100% de quimioselectividad.
Las enzimas modificadas mostraron una mayor actividad en los sistemas de células enteras en comparación con las formas purificadas.
La enantiopreferencia ajustable permitió la producción de cualquiera de los enantiómeros.

Conclusiones:

Estableció una plataforma bacteriana codificada por ADN para la borilación.
Logró un volumen de negocios catalítico más de 400 veces mayor que los catalizadores quirales existentes.
Demostró el potencial para expandir las aplicaciones de la química del boro dentro de los sistemas vivos.

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