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Cu (II) - Aminometilación orto-selectiva catalizada de los fenoles

Jin-Ling Dai¹, Nan-Qi Shao¹, Jin Zhang²

¹CAS Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, University of Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, China.

Journal of the American Chemical Society

|August 15, 2017

Resumen

Una nueva reacción catalizada por cobre permite la funcionalización orto-selectiva de los fenoles utilizando trifluoroboratos. Este método produce eficientemente valiosos productos de acoplamiento C_sp2-C_sp3 en condiciones suaves.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

La funcionalización selectiva de los fenoles es crucial en la síntesis orgánica.
El desarrollo de métodos suaves y eficientes para la formación de enlaces C-C es un desafío continuo.
La catálisis del cobre ofrece una plataforma versátil para diversas transformaciones orgánicas.

Objetivo del estudio:

Desarrollar una nueva reacción catalizada por Cu (II) para la funcionalización orto-selectiva de fenoles libres.
Para lograr el acoplamiento C_sp2-C_sp3 con los aminometiltrifluoroboratos de potasio.
Proporcionar una síntesis sencilla de fenoles sustituidos por ortoaminometilo y compuestos relacionados.

Principales métodos:

Para la reacción se empleó la catálisis del cobre.
Los fenoles libres reaccionaron con los aminometiltrifluoroboratos de potasio.
La reacción fue optimizada para condiciones suaves y un amplio alcance de sustrato.

Principales resultados:

El protocolo desarrollado logró la funcionalización orto-selectiva de los fenoles.
Una variedad de grupos funcionales en ambos sustratos fueron compatibles.
Los productos se obtuvieron en rendimientos de moderados a excelentes.
Se propuso un mecanismo de acoplamiento radical de transferencia de un solo electrón.

Conclusiones:

Se estableció un nuevo método catalizado por Cu (II) para el acoplamiento orto-selectivo C_sp2-C_sp3 de fenoles con trifluoroboratos.
El protocolo ofrece condiciones suaves y una amplia tolerancia de grupo funcional.
Esto proporciona un acceso eficiente a valiosos fenoles sustituidos por ortoaminometilo, aminoácidos no naturales y moléculas bioactivas.

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