The first anionic thia-fries rearrangements at ferrocene

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

authored by: 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.
Organisation(s): Institute of Organic Chemistry
External Organisation(s): Max-Planck-Institut für Kohlenforschung
Type: Article
Journal: Advanced Synthesis and Catalysis
Volume: 352
Pages: 1345-1355
No. of pages: 11
ISSN: 1615-4150
Publication date: 20.05.2010
Publication status: Published
Peer reviewed: Yes
ASJC Scopus subject areas: Catalysis, Organic Chemistry
Electronic version(s): https://doi.org/10.1002/adsc.201000068 (Access: Unknown)

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",
}