The first anionic thia-fries rearrangements at ferrocene

Ready access to trifluoromethylsulfonyl-substituted hydroxyferrocenes and an extremely high interannular stereoinduction between cyclopentadienyl ligands

verfasst von: Georg Werner, Christian W. Lehmann, Holger Butenschön
Abstract: Attempts originally directed towards the generation of ferrocyne (1,2-dehydroferrocene, 4) and ferrocenediyne (l,2,1′,2′- tetradehydroferrocene, 5) by triflate elimination from the respective ferrocenyl inflates led to the discovery of the first anionic thia-Fries rearrangements at a five-membered ring. These reactions take place with remarkable efficiency under very mild reaction conditions and yield the respective trifluoromethylsulfonyl-substituted ferrocenols. Most remarkably, the reaction starting from 1,1′-ferrocenediyl ditriflate (9) adopts an extremely high interannular stereoinduction in that exclusively the meso rearrangement product, meso-2,2′-bis(trifluoromethylsulfonyl)-1,1′-ferrocenediol (16), is formed, the corresponding racemic product 17 is not observed. It is shown that the second anionic thia-Fries rearrangement proceeds at a much larger rate than the first one. The stereochemistry and the high rate of this reaction are explained on the basis of electronic as well as steric considerations. The redox behavior of some of the unprecedented ferrocene derivatives has been characterized by cyclovoltammetry.
Organisationseinheit(en): Institut für Organische Chemie
Externe Organisation(en): Max-Planck-Institut für Kohlenforschung
Typ: Artikel
Journal: Advanced Synthesis and Catalysis
Band: 352
Seiten: 1345-1355
Anzahl der Seiten: 11
ISSN: 1615-4150
Publikationsdatum: 20.05.2010
Publikationsstatus: Veröffentlicht
Peer-reviewed: Ja
ASJC Scopus Sachgebiete: Katalyse, Organische Chemie
Elektronische Version(en): https://doi.org/10.1002/adsc.201000068 (Zugang: Unbekannt)

BibTeX

@article{b09dcc87d7f24b4190b7b5554a7c7925,
title = "The first anionic thia-fries rearrangements at ferrocene: Ready access to trifluoromethylsulfonyl-substituted hydroxyferrocenes and an extremely high interannular stereoinduction between cyclopentadienyl ligands",
abstract = "Attempts originally directed towards the generation of ferrocyne (1,2-dehydroferrocene, 4) and ferrocenediyne (l,2,1′,2′- tetradehydroferrocene, 5) by triflate elimination from the respective ferrocenyl inflates led to the discovery of the first anionic thia-Fries rearrangements at a five-membered ring. These reactions take place with remarkable efficiency under very mild reaction conditions and yield the respective trifluoromethylsulfonyl-substituted ferrocenols. Most remarkably, the reaction starting from 1,1′-ferrocenediyl ditriflate (9) adopts an extremely high interannular stereoinduction in that exclusively the meso rearrangement product, meso-2,2′-bis(trifluoromethylsulfonyl)-1,1′-ferrocenediol (16), is formed, the corresponding racemic product 17 is not observed. It is shown that the second anionic thia-Fries rearrangement proceeds at a much larger rate than the first one. The stereochemistry and the high rate of this reaction are explained on the basis of electronic as well as steric considerations. The redox behavior of some of the unprecedented ferrocene derivatives has been characterized by cyclovoltammetry.",
keywords = "Anionic thia-fries rearrangement, Ferrocenes, Ferrocenyl triflate, Ferrocyne, Transannular stereoinduction",
author = "Georg Werner and Lehmann, {Christian W.} and Holger Butensch{\"o}n",
year = "2010",
month = may,
day = "20",
doi = "10.1002/adsc.201000068",
language = "English",
volume = "352",
pages = "1345--1355",
journal = "Advanced Synthesis and Catalysis",
issn = "1615-4150",
publisher = "Wiley-VCH Verlag",
number = "8",
}