Cyclopentadienyl ring metalation in cyclopentadienyliron carbonyl complexes

Orlova, T. Yu.; Setkina, V. N.; Sizoi, V. F.; Kursanov, D. N.

doi:10.1016/0022-328x(83)80084-9

Cited by 22 publications

(3 citation statements)

References 6 publications

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“…The following experiments verified that the lithiation of the Cp ring by the excess amount of RLi , did not occur under the present reaction conditions. Treatment of 1a with only 1.0 equiv of PhLi was followed by quenching with D 2 O (eq ).…”

supporting

confidence: 74%

“…The reactions of [CpFe(CO) 2 Ar] with organometallic reagents are rare. The reaction of [CpFe(CO) 2 Ph] with excess butyllithium in THF at −78 °C was reported, leading to the lithiation of the cyclopentadienyl ring (eq ). , To our surprise, a similar reaction at a higher reaction temperature led to a completely different outcome. Treatment of [CpFe(CO) 2 (4-tolyl)] ( 1a ) with 2 equiv of butyllithium at −20 °C afforded butyl 4-tolyl ketone ( 2a ) in 59% yield (Table , entry 1).…”

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confidence: 85%

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Use of Aryliron Complexes [CpFe(CO)₂Ar] as Arylcarbonyl Cation Equivalents in the Reactions with Organolithium Reagents To Yield Ketones

2009

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Treatment of aryliron complexes [CpFe(CO) 2 Ar] with organolithium reagents RLi in THF affords the corresponding ketones RCOAr. The reaction, wherein the aryliron complexes serve as arylcarbonyl cation equivalents, would begin with nucleophilic addition of RLi to one of the carbonyl ligands to form acyliron [CpFe(CO)(RCO)Ar] without lithiation of the Cp ring. Dicarbonylcyclopentadienylorganoiron complexes [CpFe-(CO) 2 R] represent an important class of organometallic compounds due to their rich coordination chemistry. 1 The corresponding aryliron complexes [CpFe(CO ) 2 Ar] are fundamental 18-electron arylmetals, and several reliable methods for the synthesis of the aryliron complexes have been reported. 2 On the other hand, the chemical reactivity of the aryliron complexes has not been well investigated. [3][4][5][6][7][8] Thanks to the ubiquity and abundance of iron as a transition metal, we have envisioned that [CpFe(CO) 2 Ar] would serve as interesting arylating agents in organic synthesis and have been studying the reactivity and utility of [CpFe(CO) 2 Ar]. 2e,2f

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confidence: 74%

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confidence: 85%

Use of Aryliron Complexes [CpFe(CO)₂Ar] as Arylcarbonyl Cation Equivalents in the Reactions with Organolithium Reagents To Yield Ketones

2009

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“…Organoiron complexes bearing a dicarbonylcyclopentadienyliron moiety [CpFe(CO) 2 R] are utilized as useful organometallic reagents in organic synthesis . Among them, the reactions of the corresponding aryliron complexes [CpFe(CO) 2 Ar] are still unexplored. − Studies on chemical reactivity of [CpFe(CO) 2 Ar] provide useful organic reactions because they are expected to show different reactivity from other arylmetal reagents. Recently, we have developed the efficient synthesis of [CpFe(CO) 2 Ar] and have been pursuing their synthetic utility as useful arylmetal reagents. , In the course of these studies, we now report that [CpFe(CO) 2 Ar] react with styrenes to yield the corresponding stilbenes. , The reaction begins with insertion of the CC bond of styrene into the aryl−iron bond.…”

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confidence: 99%

Arylation of Styrenes with Aryliron Complexes [CpFe(CO)₂Ar]

2010

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Reactions of (cyclopentadienyl)rhenium halide complexes (η⁵‐C₅H₅)Re(NO)(PPh₃)(X) with n‐BuLi/TMEDA; Generation and Methylation of Lithio‐ and Dilithiocyclopentadienyl Ligands

Gladysz

1988

Chem. Ber.

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There has been a great deal of recent interest in reactions of cyclopentadienyl transition-metal complexes with strong bases such as lithium alkyls and lithium dialkylamides' -*I. Both synthetically useful' -41 and mechanistically novel '-*I processes have been discovered. Often, cyclopentadienyl ligand deprotonation occurs, giving a lithiocyclopentadienyl ligand (eq i, step a). Depending upon the nature of the rcmaining ligands, subscquent rearrangement to a metal centered anion can occur (eq i, step b)5 -*I. lhesc migrations are now known to be relatively common, and resemble wcll-established anionic rearrangements of organic compounds9'.

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Cyclopentadienyl ring metalation in cyclopentadienyliron carbonyl complexes

Cited by 22 publications

References 6 publications

Use of Aryliron Complexes [CpFe(CO)₂Ar] as Arylcarbonyl Cation Equivalents in the Reactions with Organolithium Reagents To Yield Ketones

Use of Aryliron Complexes [CpFe(CO)₂Ar] as Arylcarbonyl Cation Equivalents in the Reactions with Organolithium Reagents To Yield Ketones

Arylation of Styrenes with Aryliron Complexes [CpFe(CO)₂Ar]

Reactions of (cyclopentadienyl)rhenium halide complexes (η⁵‐C₅H₅)Re(NO)(PPh₃)(X) with n‐BuLi/TMEDA; Generation and Methylation of Lithio‐ and Dilithiocyclopentadienyl Ligands

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Cyclopentadienyl ring metalation in cyclopentadienyliron carbonyl complexes

Cited by 22 publications

References 6 publications

Use of Aryliron Complexes [CpFe(CO)2Ar] as Arylcarbonyl Cation Equivalents in the Reactions with Organolithium Reagents To Yield Ketones

Use of Aryliron Complexes [CpFe(CO)2Ar] as Arylcarbonyl Cation Equivalents in the Reactions with Organolithium Reagents To Yield Ketones

Arylation of Styrenes with Aryliron Complexes [CpFe(CO)2Ar]

Reactions of (cyclopentadienyl)rhenium halide complexes (η5‐C5H5)Re(NO)(PPh3)(X) with n‐BuLi/TMEDA; Generation and Methylation of Lithio‐ and Dilithiocyclopentadienyl Ligands

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Use of Aryliron Complexes [CpFe(CO)₂Ar] as Arylcarbonyl Cation Equivalents in the Reactions with Organolithium Reagents To Yield Ketones

Use of Aryliron Complexes [CpFe(CO)₂Ar] as Arylcarbonyl Cation Equivalents in the Reactions with Organolithium Reagents To Yield Ketones

Arylation of Styrenes with Aryliron Complexes [CpFe(CO)₂Ar]

Reactions of (cyclopentadienyl)rhenium halide complexes (η⁵‐C₅H₅)Re(NO)(PPh₃)(X) with n‐BuLi/TMEDA; Generation and Methylation of Lithio‐ and Dilithiocyclopentadienyl Ligands