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Hacia la anti-Markovnikov 1-Alkyne O-Phosphoramidation: explotando la cooperatividad de metales y ligandos en un

Marcus W Drover¹, Jennifer A Love¹, Laurel L Schafer¹

¹Department of Chemistry, The University of British Columbia , 2036 Main Mall, Vancouver, British Columbia, Canada V6T 1Z1.

Journal of the American Chemical Society

|June 22, 2016

Resumen

Este estudio introduce una nueva reacción catalizada por iridio para la O-fosforamidación de los alquinos. El método permite la formación selectiva de enlaces C-O, ofreciendo control sobre la funcionalidad a través del ligando y la elección del metal.

Área de la Ciencia:

Química organometálica
Catálisis
Química orgánica sintética

Sus antecedentes:

La cooperación entre metales y ligandos es crucial para desarrollar nuevas transformaciones catalíticas.
Los ligandos de fosforamidato ofrecen propiedades de coordinación únicas para los centros metálicos.
El control de la regioselectividad en la funcionalización de las alquinas sigue siendo un desafío clave.

Objetivo del estudio:

Desarrollar un protocolo catalítico para la O-fosforamización intermolecular de las 1-alquinas.
Investigar la cooperación metal-ligando entre el iridio (III) y los ligandos del fosforamidato.
Para lograr la formación selectiva de enlaces C-O y explorar la funcionalidad anti-Markovnikov.

Principales métodos:

Utilizando complejos de iridio (III) con ligandos fosforamidados quelatantes de 1,3-N,O.
Utilizando la O-fosforamidación intermolecular de las 1-alquinas.
Caracterización de los productos intermedios reactivos, incluidos los que implican la hemilabilidad del ligando.

Principales resultados:

Se estableció un protocolo selectivo de formación de enlaces C-O para la O-fosforamidación de 1-alquinas.
Se ha demostrado el control de la funcionalización N- versus O por selección de ligandos y metales.
Conocimiento avanzado de la O-fosforamización catalítica anti-Markovnikov mediante el uso de iridio (III).

Conclusiones:

La cooperación entre metales y ligandos permite la O-fosforamidación selectiva de las alquinas.
El protocolo desarrollado ofrece una nueva ruta para la formación de enlaces CO.
Los conocimientos sobre los productos intermedios reactivos constituyen una base para un mayor desarrollo catalítico.

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