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Transannular Addition of Phenols to 1,1′‐Dialkynylferrocenes: Unanticipated Formation of Phenoxy[4]ferrocenophanedienes
Author(s) -
Ma Jingxiang,
Kühn Björn,
Hackl Thomas,
Butenschön Holger
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200902492
Subject(s) - thiophenol , phenols , chemistry , reactivity (psychology) , acetic acid , medicinal chemistry , reaction mechanism , context (archaeology) , organic chemistry , computational chemistry , catalysis , medicine , paleontology , alternative medicine , pathology , biology
Abstract The reaction of some 1,1′‐dialkynylferrocenes with a variety of phenols in the presence as well as in the absence of [Mo(CO) 6 ] yields good to high yields of phenoxy[4]ferrocenophanedienes. Similar reactivity was observed with a thiophenol and with acetic acid. Reaction under basic reaction conditions led to the formation of the [4]ferrocenophanone 17 . The phenoxy[4]ferrocenophanedienes obtained show dynamic behavior as a result of a torsional twist of the carbon bridge as indicated by the 1 H and 13 C NMR spectra. The reaction mechanism is discussed in view of recent related results of Sato et al. as well as of Pudelski et al. A vinyl cation intermediate is postulated in this context, whose relative stability is evident from the mass spectra of the compounds prepared.