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Updated: Mar 17, 2026

A Customizable Approach for the Enzymatic Production and Purification of Diterpenoid Natural Products

A Customizable Approach for the Enzymatic Production and Purification of Diterpenoid Natural Products

Published on: October 4, 2019

Descubrimiento basado en el genoma de un modo de ciclización sin precedentes en la biosíntesis de sesterpenoides de

Masahiro Okada¹, Yudai Matsuda¹, Takaaki Mitsuhashi¹

¹Graduate School of Pharmaceutical Sciences, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

Journal of the American Chemical Society

|July 23, 2016

Resumen

Los investigadores descubrieron el quiannulateno, un nuevo sesterterpeno, utilizando la enzima fúngica EvQS. Su biosíntesis única implica reordenamientos complejos, expandiendo la diversidad conocida de los sesterterpenoides.

Área de la Ciencia:

Química de los productos naturales
Enzimología
Biosíntesis

Sus antecedentes:

Los sesterterpenoides, derivados del pirofosfato de geranilfarnesilo (GFPP), son terpenoides raros con estructuras diversas.
Muchos andamios sesterterpenoides permanecen sin descubrir debido al conocimiento limitado de sus vías biosintéticas.

Objetivo del estudio:

Para caracterizar el hongo sesterterpeno sintasa EvQS.
Descubrir y dilucidar la estructura y la biosíntesis de nuevos sesterterpenoides.

Principales métodos:

Minería del genoma para identificar las posibles síntases de sestertereno.
Ensayos enzimáticos mediante el EvQS con GFPP.
Elucidación estructural del sesterterpeno resultante.
Estudios mecanicistas del proceso de ciclización.

Principales resultados:

Se caracterizó la sesterterpena sintasa EvQS de hongos.
Se obtuvo un nuevo sesterterpeno, el quiannulateno (1), con un esqueleto de carbono único y congestionado.
El ácido quianulático (2) fue identificado como un producto oxidado del quianulateno.
La biosíntesis del quianulateno implica un modo de ciclización sin precedentes con múltiples desplazamientos de hidrógeno y migraciones de enlaces C-C.

Conclusiones:

EvQS cataliza la formación de quianulateno a través de una nueva vía de biosíntesis.
Este descubrimiento amplía la diversidad estructural conocida de los sesterterpenoides.
Los hallazgos proporcionan información sobre la evolución de la biosíntesis de terpenos.

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