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La inserción de alquino intermolecular catalizado por níquel en las ciclobutanonas

Masahiro Murakami¹, Shinji Ashida, Takanori Matsuda

¹Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan. murakami@sbchem.kyoto-u.ac.jp

Journal of the American Chemical Society

|May 12, 2005

Resumen

Los catalizadores de níquel (0) permiten que las ciclobutanonas y las alquinas formen ciclohexenonas a través de la ciclización oxidativa. Esta reacción inserta alquinas en las ciclobutanonas, creando valiosos esqueletos carbocíclicos de seis miembros de manera eficiente.

Área de la Ciencia:

Química orgánica es la química orgánica.
Química organometálica Química orgánica de los metales.
La catálisis de la catálisis.

Sus antecedentes:

Las ciclobutanonas son cetonas cíclicas de cuatro miembros.
Las alquinas son hidrocarburos insaturados que contienen enlaces triples carbono-carbono.
La síntesis eficiente de compuestos carbocíclicos de seis miembros es crucial en la química orgánica.

Objetivo del estudio:

Desarrollar una nueva ruta sintética para las ciclohexenoles.
Para explorar la reactividad de las ciclobutanonas con las alquinas utilizando la catálisis del níquel.
Para lograr la inserción formal de alquinos en las ciclobutanonas.

Principales métodos:

Reacción de las ciclobutanonas con varios alquinas.
Utilizando complejos de níquel (((0) como catalizadores.
Empleando ciclización oxidativa y mecanismos de eliminación reductora.

Principales resultados:

Síntesis exitosa de ciclohexenonas sustituidas a partir de ciclobutanonas y alquinas.
Demostración de una inserción formal de alquina entre el carbonio y el carbono alfa de las ciclobutanonas.
Identificación de los pasos mecánicos clave, incluida la ciclización oxidativa y la eliminación de beta-carbono.

Conclusiones:

La reacción catalizada por níquel (0) proporciona un método eficaz para la construcción de anillos carbocíclicos de seis miembros.
La reacción ofrece una nueva vía para la funcionalización de las ciclobutanonas y las alquinas.
Esta metodología expande la utilidad sintética de las ciclobutanonas en la síntesis orgánica.

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