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Ciclización transanular inducida por la dearomatización: síntesis de tiofeno-S, dióxido de S, bifenileno fusionado

Aiko Fukazawa¹, Hiroya Oshima, Soji Shimizu

¹Department of Chemistry, Graduate School of Science and ‡Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University , Furo, Chikusa, Nagoya 464-8602, Japan.

Journal of the American Chemical Society

|June 7, 2014

Resumen

La oxidación de los deshidroanulenos fusionados con tiofeno desencadena una rápida ciclización transanular, formando nuevos hidrocarburos aromáticos policíclicos. Este interruptor de reactividad, impulsado por cambios en la aromaticidad, permite una síntesis eficiente de derivados únicos del bifenileno.

Área de la Ciencia:

Química orgánica es la química orgánica.
Ciencia de los materiales Ciencia de los materiales.
Química supramolecular de las moléculas.

Sus antecedentes:

La ciclización transanular de los deshidroanulenos es un método clave para la síntesis de hidrocarburos aromáticos policíclicos (HAP).
La reactividad de estos sistemas está influenciada por la aromaticidad de las estructuras de anillo fundido.

Objetivo del estudio:

Investigar el efecto de la aromaticidad en la ciclización transanular de los dehidroanulenos fusionados con tiofeno.
Para sintetizar y caracterizar nuevos hidrocarburos aromáticos policíclicos con propiedades electrónicas únicas.

Principales métodos:

Oxidación del bisdehidro[12]annuleno fusionado con tiofeno utilizando el ácido m-cloroperbenzoico.
Estudios experimentales y teóricos (por ejemplo, análisis de reacciones electrocíclicas) para elucidar los mecanismos de reacción.
Caracterización de los productos de hidrocarburos aromáticos policíclicos resultantes.

Principales resultados:

La oxidación de los anillos de tiofeno a tiofeno-S,S-dióxidos indujo una rápida ciclización transanular a temperatura ambiente, formando un conducto de carga de ciclo [2+2].
La ciclización térmica del precursor no oxidado requirió un calentamiento prolongado (80 °C durante 9 días).
El derivado de bifenileno sintetizado de tiofeno-S, S-dióxido fusionado exhibió una mayor afinidad electrónica y una fuerte fluorescencia.

Conclusiones:

La aromaticidad de los anillos fundidos afecta significativamente la reactividad de los deshidroanulenos, permitiendo un cambio en las vías de ciclización.
La oxidación proporciona una ruta fácil para activar los deshidroanulenos para una rápida ciclización.
El nuevo derivado del bifenileno posee propiedades optoelectrónicas prometedoras para aplicaciones de materiales.

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