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Arilsulfonilacetamidas como reactivos bifuncionales para la aminoariación de alquenos
Timothy M Monos1, Rory C McAtee1, Corey R J Stephenson2
1Department of Chemistry, University of Michigan, Ann Arbor, MI, USA.
Science (New York, N.Y.)
|September 29, 2018
Resumen
Un nuevo método catalítico permite la síntesis de 2,2-diariletilaminas a través de la aminoariación de alquenos utilizando arilsulfonilacetamidas. Esta reacción impulsada por la luz visible es eficiente, selectiva y utiliza materiales fácilmente disponibles.
Área de la Ciencia:
- Química orgánica
- Química sintética
- Catálisis
Sus antecedentes:
- La aminoarilación de alceno es una transformación clave en la síntesis orgánica.
- El desarrollo de métodos concisos y eficientes para la construcción de enlaces C-N es crucial.
- Los métodos existentes a menudo requieren múltiples pasos o condiciones difíciles.
Objetivo del estudio:
- Desarrollar un nuevo protocolo catalítico para la aminoarilación de alquenos.
- Para lograr una regioselectividad anti-Markovnikov y una alta diastereoselectividad en la adición de arilsulfonilacetamidas a los alquenos.
- Para establecer una reacción de oxidación-reducción impulsada por la luz visible para sintetizar 2,2-diariletilaminas.
Principales métodos:
- Adición catalítica de arilsulfonilacetamidas a los alquenos ricos en electrones.
- Utilizando un solo reactivo bifuncional para la formación de enlaces C-N.
- Utilizando la catálisis fotorredóxica de luz visible para permitir la oxidación de un solo electrón de alqueno.
Principales resultados:
- Se logró una completa regioselectividad anti-Markovnikov.
- Se observó una excelente diastereoselectividad, produciendo 2,2-diariletilaminas.
- La reacción se produce a temperatura ambiente con pérdida de dióxido de azufre y amplia compatibilidad del grupo funcional.
Conclusiones:
- El protocolo desarrollado ofrece una estrategia sintética concisa y eficiente para las 2,2-diariletilaminas.
- El mecanismo de reacción involucra a un radical bencílico intermedio clave que se somete a un desplazamiento de Smiles-Truce 1,5-arilo.
- Este proceso mediado por luz visible es muy adecuado para diversas aplicaciones sintéticas debido a sus condiciones suaves y materiales de partida fácilmente disponibles.
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