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Dicarboxilación electroquímica de los heterociclos con potenciales de reducción muy negativos

Yong You^1,2, Wataru Kanna³, Hideaki Takano^1,2

¹Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan.

Journal of the American Chemical Society

|February 22, 2022

Resumen

Este estudio introduce un método electroquímico para la dicarboxilación dearomativa de los heteroaromáticos utilizando dióxido de carbono (CO2). Este eficiente proceso produce valiosos ácidos dicarboxílicos para sintetizar moléculas biológicamente activas.

Área de la Ciencia:

Química orgánica
La electroquímica
Química sintética

Sus antecedentes:

La dicarboxilación de los heteroaromáticos estables mediante el uso de dióxido de carbono (CO2) es una transformación difícil.
Los métodos existentes carecen de eficiencia y concisión para producir ácidos dicarboxílicos sintéticamente útiles.
Los ácidos dicarboxílicos son importantes intermediarios para los productos naturales y las drogas.

Objetivo del estudio:

Desarrollar un nuevo protocolo electroquímico para la dicarboxilación dearomativa de heteroaromáticos.
Para sintetizar valiosos intermediarios de ácido dicarboxílico para compuestos biológicamente activos.
Para explorar estrategias de monocarboxilación selectiva.

Principales métodos:

Reducción electroquímica del dióxido de carbono (CO2) a su anión radical.
Dicarboxilación de indoles protegidos por N y otros heteroaromáticos con potenciales de reducción muy negativos.
La monocarboxilación selectiva se logra mediante el control del electrolito, el disolvente y los aditivos protóticos.

Principales resultados:

Síntesis sin precedentes de ácidos 2,3-dicarboxílicos trans-orientados a partir de indoles protegidos por N.
Dicarboxilación exitosa de varios heteroaromáticos con potenciales de reducción de hasta -3 V.
Se ha demostrado la monocarboxilación selectiva, dando lugar a un derivado del ácido octahidroindole-2-carboxílico.

Conclusiones:

Un nuevo y eficiente protocolo electroquímico permite la dicarboxilación dearomativa de diversos heteroaromáticos utilizando CO2.
Los ácidos dicarboxílicos sintetizados sirven como intermediarios versátiles para moléculas biológicamente activas.
La metodología ofrece una vía para la monocarboxilación selectiva, ampliando la utilidad sintética.

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