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Tiolación selectiva del sitio de los heteroarenos (multi) halogenados

Frederik Sandfort¹, Tobias Knecht¹, Tobias Pinkert¹

¹Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149 Münster, Germany.

Journal of the American Chemical Society

|April 3, 2020

Resumen

Un nuevo método fotocatalítico permite la tiolación selectiva del sitio de los heteroarenos ricos en electrones. Este enfoque permite la formación de enlaces carbono-azufre en el sitio más rico en electrones, ofreciendo una estrategia complementaria a los métodos existentes.

Área de la Ciencia:

Química orgánica
Fotocatálisis
Química medicinal

Sus antecedentes:

La tiolación de los heteroarenos es crucial para la síntesis de compuestos farmacéuticamente activos.
Los métodos existentes a menudo carecen de selectividad del sitio o requieren condiciones duras.
El desarrollo de estrategias de acoplamiento C-S suaves y selectivas sigue siendo un objetivo importante.

Objetivo del estudio:

Informar sobre una estrategia general y simple para la tiolación selectiva del sitio de los heteroarenos ricos en electrones.
Establecer un protocolo fotocatalítico suave y confiable para el acoplamiento C-S.
Complementar las metodologías establecidas para la funcionalización heteroarena.

Principales métodos:

Tiolación fotocatalítica con tiolos.
Utilizando como sustratos heteroarenos (multi) halogenados ricos en electrones.
Utilizando estudios experimentales y computacionales para dilucidar el mecanismo de reacción.

Principales resultados:

Se ha logrado el acoplamiento selectivo del sitio C-S en la posición más rica en electrones de los heteroarenos.
Demostró la generalidad y simplicidad del protocolo.
Se identificó un mecanismo de cadena radical que implica la sustitución aromática homolítica por un radical tilio.

Conclusiones:

El protocolo fotocatalítico presentado ofrece un método eficiente y selectivo para la tiolación del heteroareno.
Los hallazgos ponen de relieve un modo de reactividad subdesarrollado en la formación de enlaces C-S.
Esta estrategia proporciona una herramienta valiosa para la química medicinal y el descubrimiento de fármacos.

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