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Cicloadición selectiva [2σ + 2σ] habilitada por catálisis de radicales de boronilo: síntesis de ciclo[3.1.1]heptanos

Tao Yu¹, Jinbo Yang², Zhijun Wang²

¹Frontier Institute of Science and Technology and State Key Laboratory for Mechanical Behavior of Materials, Xi'an Jiaotong University, Xi'an 710054, China.

Journal of the American Chemical Society

|February 10, 2023

Resumen

Una nueva reacción de cicloadición radical [2σ + 2σ] permite una síntesis eficiente de derivados de biciclo [3.1.1] heptano. Este método ofrece una ruta modular y atómica a valiosos bioisósteros 3D y esqueletos de terpenos.

Área de la Ciencia:

Química orgánica
Metodología sintética
Catálisis

Sus antecedentes:

Las reacciones de cicloadición tradicionales generalmente involucran enlaces π.
Los biciclo[1.1.0]butanos (BCB) y las cetonas de ciclopropilo son bloques de construcción valiosos.
Los derivados sustituidos de biciclo[3.1.1]heptano (BCH) son importantes bastidores en productos naturales y en la química medicinal.

Objetivo del estudio:

Desarrollar una nueva reacción de cicloadición radical [2σ + 2σ].
Establecer una ruta sintética modular, concisa y de economía atómica para los derivados BCH sustituidos.
Para explorar el sistema catalítico para esta transformación.

Principales métodos:

Cicloadición radical entre los BCB y las cetonas de ciclopropilo.
Catalización mediante el uso de un compuesto tetraalcoxidiborón (B₂pin₂) y isonicotinato de 3-pentilo.
Síntesis y caracterización de derivados de BCH altamente funcionalizados.

Principales resultados:

Desarrollo exitoso de una reacción de cicloadición radical [2σ + 2σ].
Se demostró un amplio alcance de sustrato, dando lugar a BCH funcionalizados con hasta seis sustituyentes.
Se obtienen altos rendimientos aislados, hasta el 99%.

Conclusiones:

La reacción desarrollada proporciona un método eficiente y versátil para sintetizar derivados de BCH.
Los estudios computacionales aclararon un ciclo catalítico de radicales de boronilo asistido por piridina.
Esta metodología expande la caja de herramientas sintéticas para acceder a arquitecturas moleculares complejas.

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