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Fosfinación electrofílica libre de metales y ciclización de los alquinos

Yuto Unoh¹, Koji Hirano¹, Masahiro Miura¹

¹Department of Applied Chemistry, Graduate School of Engineering, Osaka University , Suita, Osaka 565-0871, Japan.

Journal of the American Chemical Society

|April 18, 2017

Resumen

Una nueva reacción libre de metales permite la fosfinación electrofílica utilizando óxidos de fosfina secundarios. Este método sintetiza eficientemente los productos de ciclización fosfinados de las alquinas y los nucleófilos colgantes.

Área de la Ciencia:

Química orgánica
Química de los organofosforos

Sus antecedentes:

Los sistemas catalíticos libres de metales son muy deseables en la síntesis orgánica.
Las reacciones de fosfinación electrofílica son cruciales para la introducción de fósforo en las moléculas orgánicas.

Objetivo del estudio:

Desarrollar una nueva reacción de fosfinación electrofílica libre de metales.
Para sintetizar de manera eficiente los productos de ciclización con fosfina.

Principales métodos:

Generación in situ de especies de fósforo electrófilas a partir de óxidos de fosfina secundarios y anhídrido trifílico (Tf2O).
Acoplamiento de estas especies con alquinas que tienen nucleófilos colgantes.

Principales resultados:

Desarrollo exitoso de una reacción de fosfinación electrofílica libre de metales.
Se obtuvieron buenos rendimientos de productos de ciclización fosfinados.
Los estudios preliminares de RMN sugieren la participación de los intermediarios de fosfirenio.

Conclusiones:

El método desarrollado ofrece una nueva vía para la fosfinación sin metales.
La reacción proporciona acceso a valiosos productos de ciclización fosfinados.
Se necesitan más investigaciones mecanicistas para confirmar el papel de las especies de fosfirenio.

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