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The first anionic thia-fries rearrangements at ferrocene: Ready access to trifluoromethylsulfonyl-substituted hydroxyferrocenes and an extremely high interannular stereoinduction between cyclopentadienyl ligands

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Original languageEnglish
Pages (from-to)1345-1355
Number of pages11
JournalAdvanced Synthesis and Catalysis
Volume352
Issue number8
Publication statusPublished - 20 May 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.

Keywords

    Anionic thia-fries rearrangement, Ferrocenes, Ferrocenyl triflate, Ferrocyne, Transannular stereoinduction

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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",
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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

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