Surprisingly facile decomposition of the dication : a metal-mediated Hunsdiecker reaction of a succinimidyl ester?

Amouri, Hani; Gruselle, Michel; Vaissermann, Jacqueline; McGlinchey, Michael J.; Jaouen, Gérard

doi:10.1016/0022-328x(94)24772-b

Cited by 13 publications

(5 citation statements)

References 22 publications

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“…A range of sandwich complexes have been prepared for this purpose in recent years including the ferrocenylmethyl [30,31] and [(η 5 -Cp*)M{η 6 - nϩ (R ϭ N-succinimide; M ϭ Ir, n ϭ 2; M ϭ Ru, n ϭ 1) fragments. [32,33] We, therefore, prepared both [(η 6 -C 6 Me 6 )Ru(η 6 -ppa)](OTf) 2 and [(η 6 -C 6 Me 6 )Ru(η 6 -pba)](OTf) 2 (10) as potential N-terminal labels for peptides. However, preliminary reactivity studies indicated that yields of coupling products for the former complex would be at best very low, as also observed for [(η 5 -Cp*)Ir(η 6 -CH 3 OC 6 H 4 CH 2 COOR)](BF 4 ) 2 (R ϭ N-succinimide) [32] which also only has one CH 2 group in its pendant arm.…”

Section: Amino Acid and Peptide Labellingmentioning

confidence: 99%

“…[32,33] We, therefore, prepared both [(η 6 -C 6 Me 6 )Ru(η 6 -ppa)](OTf) 2 and [(η 6 -C 6 Me 6 )Ru(η 6 -pba)](OTf) 2 (10) as potential N-terminal labels for peptides. However, preliminary reactivity studies indicated that yields of coupling products for the former complex would be at best very low, as also observed for [(η 5 -Cp*)Ir(η 6 -CH 3 OC 6 H 4 CH 2 COOR)](BF 4 ) 2 (R ϭ N-succinimide) [32] which also only has one CH 2 group in its pendant arm. Further investigations were, therefore, restricted to the 4-phenylbutyric acid complex 10, which was prepared by reaction of [(η 6 -pba)Ru(acetone) 3 ](OTf) 2 with C 6 Me 6 in trifluoroacetic acid.…”

Section: Amino Acid and Peptide Labellingmentioning

confidence: 99%

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Preparation, Reactivity and Peptide Labelling Properties of (η⁶‐Arene)ruthenium(II) Complexes with Pendant Carboxylate Groups

et al. 2003

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Abstract(η6‐Arene)ruthenium(II) complexes of the type [{[η6‐C6H5(CH2)nCOOH]Ru(µ‐Cl)Cl}2] (2a, n = 1; 3, n = 3) with tethered carboxylate groups can be obtained by dehydrogenation of the appropriate cyclohexadiene with RuCl3·3H2O. Formation of a κO‐coordinated chelate in weakly acidic solution is observed by means of a 1H NMR titration for both [{η6‐C6H5(CH2)3COOH}Ru(aq)](OTf)2 (3a′) and [{η6‐C6H5(CH2)3COOH}Ru(phen)(aq)](OTf)2 (5′). Sandwich complexes of the type [{η6‐C6H5(CH2)3COOH}Ru(η6‐amino acid)](OTf)2 [amino acid = AcpheOH (6), ActyrOEt (7), ActrpOH (8)] can be prepared by treating [{η6‐C6H5(CH2)3COOH}Ru(acetone)3](OTf)2 with the appropriate aromatic bioligand in CF3COOH (6/8) or CH2Cl2 (7). Chemospecific η6‐labelling of the C‐terminal indole function is observed for the peptide HphetrpOH in the analogous complex 9. Quantitative formation of 8 can also be achieved in aqueous solution in the presence of a 3:1 excess of the {η6‐C6H5(CH2)3COOH}RuII fragment. This can also be employed for the N‐terminal labelling of amino acids and peptides in its sandwich complex [(η6‐C6Me6)Ru{η6‐C6H5(CH2)3COOH}](OTf)2 (10). Coupling reactions by the carbodiimide method with EDC afford water‐stable complexes of the type [(η6‐C6Me6)Ru{η6‐C6H5(CH2)3C(O)R}](OTf)2 [R = trpOMe (11), pheOMe (12), glyglyOEt (13)] in good yields. X‐ray structures of [(η6‐C6H5CH2COOC2H5)RuCl(phen)](OTf) (4b′) and 10 are reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Section: Amino Acid and Peptide Labellingmentioning

confidence: 99%

Section: Amino Acid and Peptide Labellingmentioning

confidence: 99%

Preparation, Reactivity and Peptide Labelling Properties of (η⁶‐Arene)ruthenium(II) Complexes with Pendant Carboxylate Groups

et al. 2003

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“…The structure of the cation [ 2b ] 2+ is close to the structure of various other (cyclopentadienyl)(arene)iridium complexes [Cp*Ir(arene)] 2+ (arene = benzene derivatives, tyrosine, phenanthrene, pyrene, etc.) . Similar to the cobalt complex [ 1 ](SbF 6 ) 2 , the fluorene ligand in [ 2b ](SbF 6 ) 2 is η 6 -coordinated to the iridium atom with considerable slippage toward C2, C3, and C4 atoms.…”

Section: Results and Discussionmentioning

confidence: 99%

Fluorene Complexes of Group 9 Metals: Fluorene Effect and Application for Reductive Amination

et al. 2019

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The η 6 -fluorene cyclopentadienyl complexes [(η 5 -C 5 R 5 )-M(η 6 -fluorene)](SbF 6 ) 2 (1: M = Co, R = Me; 2a: M = Rh, R = H; 2b: M = Ir, R = H) were synthesized by the iodide abstraction from [(η 5 -C 5 R 5 )MI 2 ] n with AgSbF 6 in the presence of fluorene. The procedure is also suitable for the synthesis of the indenyl derivatives [(η 5indenyl)M(η 6 -fluorene)](SbF 6 ) 2 (3a: M = Rh; 3b: M = Ir) starting from [(η 5 -indenyl)MI 2 ] n . The structures of [1](SbF 6 ) 2 and [2b](SbF 6 ) 2 were determined by X-ray diffraction. The rhodium complex [2a]-(SbF 6 ) 2 readily undergoes the replacement of the fluorene ligand by mesitylene, being more reactive than the benzene derivative [CpRh(η 6 -C 6 H 6)](SbF 6 ) 2 . According to experimental data and DFT calculations, the fluorene elimination proceeds via a cascade of η 6 → η 5 → η 1 haptotropic rearrangements. The complex [2b](SbF 6 ) 2 (at 1 mol % loading) effectively catalyzes the reductive amination reaction between aldehydes (or ketones) and primary aromatic (or secondary aliphatic) amines in the presence of carbon monoxide, giving the corresponding secondary and tertiary amines in the range of yields 59−91%. This protocol uses water as a solvent.

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“…Previously we reported the synthesis of a series of dicationic iridium complexes of the type [Cp*Ir(η 6 -MeOC 6 H 4 (CH 2 ) n COONS] 2+ ( n = 1, 2, 3) ( 9 − 11 ) and found that these complexes decompose during the reaction course with primary amines and amino esters …”

Section: Resultsmentioning

confidence: 99%

“…We reported previously the preparation of a series of organometallic succinimidyl esters (see Figure ) in which a [Cp*Ir] unit is coordinated at the arene possessing an alkyl chain terminated by a succinimidyl ester moiety . Such derivatives can be regarded as Bolton−Hunter reagents, in which the aryl ring bears a [Cp*Ir] moiety.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of CpRu^II η⁶-π-Adducts of Functionalized Arenes with Useful Side Chains: X-ray Molecular Structure of [CpRu(η⁶-N-succinimidyl 3-(4-methoxyphenyl)propionate)][CF₃SO₃]

1996

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Several novel organoruthenium complexes [Cp*Ru(η6-arene)][CF3SO3] (3, 4, 6) were prepared in which the arene unit possesses an alkyl chain terminated with carboxylic acid, ester, and activated ester functions. These compounds were fully characterized by spectroscopic methods, and in particular, the activated ester complex [Cp*Ru(η6-MeOC6H4(CH2)2COONS)][CF3SO3] (6) (NS = N-succinimidyl) was identified by X-ray analysis. The reactivity of 6 with respect to benzylamine and β-alanine ethyl ester was examined and afforded quantitatively the stable conjugates [Cp*Ru(η6-MeOC6H4CH2CH2CONHCH2Ph][CF3SO3] (7) and [Cp*Ru(η6-MeOC6H4(CH2)2CONH(CH2)2COOEt][CF3SO3] (8). Furthermore, the stability and reactivity of 6 relative to the analogous dicationic organoiridium complex [Cp*Ir(η6-MeOC6H4(CH2)2COONS)][BF4]2 (10) and the neutral metallocarbonyl derivatives of the type [L n MCpCOONS] (12−14) [L n M = Fe(CO)2Me, Mo(CO)3Me, Co(CO)2] are presented and discussed.

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Surprisingly facile decomposition of the dication : a metal-mediated Hunsdiecker reaction of a succinimidyl ester?

Cited by 13 publications

References 22 publications

Preparation, Reactivity and Peptide Labelling Properties of (η⁶‐Arene)ruthenium(II) Complexes with Pendant Carboxylate Groups

Preparation, Reactivity and Peptide Labelling Properties of (η⁶‐Arene)ruthenium(II) Complexes with Pendant Carboxylate Groups

Fluorene Complexes of Group 9 Metals: Fluorene Effect and Application for Reductive Amination

Synthesis and Reactivity of CpRu^II η⁶-π-Adducts of Functionalized Arenes with Useful Side Chains: X-ray Molecular Structure of [CpRu(η⁶-N-succinimidyl 3-(4-methoxyphenyl)propionate)][CF₃SO₃]

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Surprisingly facile decomposition of the dication : a metal-mediated Hunsdiecker reaction of a succinimidyl ester?

Cited by 13 publications

References 22 publications

Preparation, Reactivity and Peptide Labelling Properties of (η6‐Arene)ruthenium(II) Complexes with Pendant Carboxylate Groups

Preparation, Reactivity and Peptide Labelling Properties of (η6‐Arene)ruthenium(II) Complexes with Pendant Carboxylate Groups

Fluorene Complexes of Group 9 Metals: Fluorene Effect and Application for Reductive Amination

Synthesis and Reactivity of Cp*RuII η6-π-Adducts of Functionalized Arenes with Useful Side Chains: X-ray Molecular Structure of [Cp*Ru(η6-N-succinimidyl 3-(4-methoxyphenyl)propionate)][CF3SO3]

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Preparation, Reactivity and Peptide Labelling Properties of (η⁶‐Arene)ruthenium(II) Complexes with Pendant Carboxylate Groups

Preparation, Reactivity and Peptide Labelling Properties of (η⁶‐Arene)ruthenium(II) Complexes with Pendant Carboxylate Groups

Synthesis and Reactivity of CpRu^II η⁶-π-Adducts of Functionalized Arenes with Useful Side Chains: X-ray Molecular Structure of [CpRu(η⁶-N-succinimidyl 3-(4-methoxyphenyl)propionate)][CF₃SO₃]