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Pivalatos de carbamoilzinco estables para el acceso modular a las amidas, las ureas y los tiocarbamatos

Donghao Luo¹, Liangjie Ruan¹, Jiayi Xue¹

¹State Key Laboratory of Bioinspired Interfacial Materials Science, MOE Key Laboratory of Geriatric Diseases and Immunology, Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.

Journal of the American Chemical Society

|August 21, 2025

Resumen

Los investigadores desarrollaron pivalatos de carbamoilzinco estables a partir de formamidas para la síntesis sostenible de amidas y ureas. Este nuevo método ofrece un enfoque más ecológico para crear bloques de construcción químicos esenciales para la química medicinal.

Área de la Ciencia:

Química orgánica
Química medicinal
Química sustentable

Sus antecedentes:

Las funcionalidades de la amida y la urea son andamios cruciales en los compuestos biológicamente activos.
Los métodos sintéticos existentes a menudo se basan en reactivos peligrosos o activadores estequiométricos.
Se necesitan métodos sostenibles y eficientes para la síntesis de unidades de amida.

Objetivo del estudio:

Para desarrollar un nuevo y estable reactivo carbamoylating.
Establecer una plataforma sintética sostenible para las amidas y los compuestos relacionados.
Demostrar la utilidad del método desarrollado en química medicinal.

Principales métodos:

Preparación de pivalatos de carbamoilzinco estabilizados con sales mediante la metalización C-H de las formamidas utilizando TMPLi y Zn(OPiv) 2.
Utilizando los pivalatos de carbamoilzinco en la carbamoilación de Negishi catalizada por el paladio.
El uso de los reactivos en la aminación electrofílica catalizada por el cobre, la tiolación y la selenolación.

Principales resultados:

Se sintetizaron polvos de pivalato de carbamoilzinco estables al aire y a la humedad.
Los reactivos mostraron una alta reactividad en la carbamoilación selectiva de Negishi C-S.
Se lograron reacciones exitosas de aminación, tiolación y selenolación catalizadas por cobre.
El protocolo permitió el acceso a amidas funcionalizadas, ureas asimétricas, tiocarbamatos y selenocarbamatos.
Se demostró la modificación en etapa tardía de moléculas similares a fármacos y la síntesis directa de fármacos.

Conclusiones:

Se ha establecido una nueva plataforma sostenible para la síntesis de amida y urea utilizando reactivos estables de carbamoilzinco.
La estrategia de zincado y acoplamiento C-H desarrollada ofrece una alternativa más ecológica a los métodos tradicionales.
Esta metodología tiene un potencial significativo para aplicaciones en química medicinal y descubrimiento de fármacos.

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