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Las reacciones de reordenamiento de los 1,1-divinil-2-fenilciclopropanetos

E Ben Hay¹, Hanmo Zhang, Dennis P Curran

¹Department of Chemistry, University of Pittsburgh , Pittsburgh, Pennsylvania 15260, United States.

Journal of the American Chemical Society

|December 23, 2014

Resumen

Los 1,1-divinil-2-fenilciclopropanos se someten a diversas reorganizaciones. Las ciclizaciones de radicales en tándem y las reacciones térmicas producen vinilciclopentenos y espirolactamos tricíclicos, que muestran una rica química sintética.

Área de la Ciencia:

Química orgánica es la química orgánica.
Química sintética de la química sintética.

Sus antecedentes:

Los 1,1-divinil-2-fenilciclopropanos son precursores versátiles en la síntesis orgánica.
La química del reordenamiento ofrece vías hacia arquitecturas moleculares complejas.

Objetivo del estudio:

Para explorar la química de reordenamiento de los 1,1-divinil-2-fenilciclopropanos.
Para investigar las ciclizaciones de radicales en tándem y las isomerizaciones térmicas de sustratos de N,N-diallilamida.

Principales métodos:

Iniciación de ciclizaciones de radicales en tándem a temperatura ambiente.
Reacciones de reordenamiento térmico de sustratos con ácidos, ésteres y amidas.
Modificación del grupo carbonilo en alcoholes o éteres para estudiar las vías posteriores.

Principales resultados:

Las ciclizaciones en tándem de los radicales de N,N-diallilamidas se producen fácilmente a temperatura ambiente.
Las reorganizaciones térmicas producen vinilciclopentenos a través de reorganizaciones de divinylciclopropano.
Los reordenamientos aromáticos de Cope seguidos de reacciones de ene producen espirolactamos tricíclicos.
Las modificaciones en el grupo carbonilo permiten las vías de retro-eno, la tautomerización o los reordenamientos de Claisen.

Conclusiones:

Los 1,1-divinil-2-fenilciclopropanos son valiosos sintones para la construcción de moléculas complejas.
El estudio revela diversas vías de reacción que incluyen ciclizaciones radicales, reordenamientos térmicos y transformaciones mediadas por carbonilo.
Este trabajo amplía el alcance del divinylcyclopropano y la química de reordenamiento de Cope.

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