Higher-order cyclization reactions of alkenyl Fischer carbene complexes: A new selective all-carbon [8 + 2] cyclization with 8-methoxyheptafulvene and computational mechanistic analysis

  1. García-Rodríguez, J. 2
  2. González, Jairo. 2
  3. Santamaría, J. 2
  4. Suárez-Sobrino, Á.L. 2
  5. Rodríguez, M.A. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Universidad de Oviedo
    info

    Universidad de Oviedo

    Oviedo, España

    ROR https://ror.org/006gksa02

Revista:
Dalton Transactions

ISSN: 1477-9226

Año de publicación: 2016

Volumen: 45

Número: 28

Páginas: 11353-11361

Tipo: Artículo

DOI: 10.1039/C6DT01465H SCOPUS: 2-s2.0-84978716308 WoS: WOS:000379573200017 GOOGLE SCHOLAR

Otras publicaciones en: Dalton Transactions

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Sistemas fotoactivos: aplicaciones biológicas y de almacenamiento de energía. Photoactive systems: biological applications and energy storage.

2015/00065/001

Resumen

A new higher-order cyclization reaction of alkenyl Fischer carbene complexes is described. Chromium and tungsten alkenyl Fischer carbene complexes react toward 8-methoxyheptafulvene through an all-carbon formal [8 + 2] cycloaddition reaction with complete regio- and stereoselectivity. Tetrahydroazulene compounds bearing four consecutive stereocenters are generated. The reaction mechanism is rationalized based on computational calculations. It was found that this transformation proceeds through a concerted process. The nature of the observed stereo- and regioselectivity can be attributed to both steric and electronic factors. © The Royal Society of Chemistry 2016.