Higher-order cyclization reactions of alkenyl Fischer carbene complexes: A new selective all-carbon [8 + 2] cyclization with 8-methoxyheptafulvene and computational mechanistic analysis
- García-Rodríguez, J. 2
- González, Jairo. 2
- Santamaría, J. 2
- Suárez-Sobrino, Á.L. 2
- Rodríguez, M.A. 1
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1
Universidad de La Rioja
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2
Universidad de Oviedo
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ISSN: 1477-9226
Année de publication: 2016
Volumen: 45
Número: 28
Pages: 11353-11361
Type: Article
beta Ver similares en nube de resultadosD'autres publications dans: Dalton Transactions
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Résumé
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.