Higher-order cyclization reactions of alkenyl Fischer carbene complexes: a new selective all-carbon [8 + 2] cyclization with 8-methoxyheptafulvene and computational mechanistic analysis. Issue 28 (22nd June 2016)

• Record Type: Journal Article
• Authors: García-Rodríguez, Jaime; González, Jairo; Santamaría, Javier; Suárez-Sobrino, Ángel L.; Rodríguez, Miguel A.
• Is Part Of: Dalton transactions. Volume 45:Issue 28(2016)
• Page Start: 11353
• Page End: 11361
• Publication Date: 2016-06-22
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt01465h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A new all-carbon [8 +2] cycloaddition of alkenyl Fischer carbene complexes is described. Abstract : 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.