Details
| Originalsprache | Englisch |
|---|---|
| Seiten (von - bis) | 1345-1355 |
| Seitenumfang | 11 |
| Fachzeitschrift | Advanced Synthesis and Catalysis |
| Jahrgang | 352 |
| Ausgabenummer | 8 |
| Publikationsstatus | Veröffentlicht - 20 Mai 2010 |
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.
ASJC Scopus Sachgebiete
- Chemische Verfahrenstechnik (insg.)
- Katalyse
- Chemie (insg.)
- Organische Chemie
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in: Advanced Synthesis and Catalysis, Jahrgang 352, Nr. 8, 20.05.2010, S. 1345-1355.
Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review
}
TY - JOUR
T1 - The first anionic thia-fries rearrangements at ferrocene
T2 - Ready access to trifluoromethylsulfonyl-substituted hydroxyferrocenes and an extremely high interannular stereoinduction between cyclopentadienyl ligands
AU - Werner, Georg
AU - Lehmann, Christian W.
AU - Butenschön, Holger
PY - 2010/5/20
Y1 - 2010/5/20
N2 - 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.
AB - 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.
KW - Anionic thia-fries rearrangement
KW - Ferrocenes
KW - Ferrocenyl triflate
KW - Ferrocyne
KW - Transannular stereoinduction
UR - http://www.scopus.com/inward/record.url?scp=77952712195&partnerID=8YFLogxK
U2 - 10.1002/adsc.201000068
DO - 10.1002/adsc.201000068
M3 - Article
AN - SCOPUS:77952712195
VL - 352
SP - 1345
EP - 1355
JO - Advanced Synthesis and Catalysis
JF - Advanced Synthesis and Catalysis
SN - 1615-4150
IS - 8
ER -