(S)-Histidine: the ideal precursor for a novel family of chiral aminoacid and peptidic ionic liquids

Guillen, Frédéric; Brégeon, Delphine; Plaquevent, Jean‐Christophe

doi:10.1016/j.tetlet.2005.12.090

Cited by 45 publications

(28 citation statements)

References 15 publications

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“…Therefore, mixtures of regioisomers are obtained when the imidazole is reacted with one equivalent of an electrophile. To obtain the desired dissymmetrically substituted histidinium salts, we applied a route based on the report by Hodges and Chivikas,17 and was improved by Brégeon et al30 (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…Histidylidenes, NHCs that are derived from histidine, have only recently been explored by Erker et al24 and by Albrecht et al25–28 The alkylation of histidine was also reported in studies toward chiral ionic liquids 29,30. The publications by Albrecht et al and several other publications show that NHCs, histidylidenes, and other NHCs derived from natural compounds31–35 are highly interesting compounds for bioorganometallic applications 4,36.…”

Section: Introductionmentioning

confidence: 99%

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Allylpalladium(II) Histidylidene Complexes and Their Application in Z‐Selective Transfer Semihydrogenation of Alkynes

et al. 2015

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We have studied the use of amino acid histidine as a precursor for N-heterocyclic carbene (NHC) ligands. This natural amino acid possesses an imidazole substituent, which makes it an interesting NHC precursor that contains both an acid and an amino functionality. These functionalities may be used for further tuning of NHC complexes. We have developed routes for the synthesis of symmetric and dissymmetric alkyl, benzyl, and aryl-substituted histidinium salts.[a] Molecular Scheme 3. Synthesis of symmetrically substituted benzylic histidinium bromides. The Cyclic Urea ApproachSubsequently, we employed the cyclic urea approach, which allows the synthesis of dissymmetrically substituted histidinium salts and further tuning of the properties of the NHC metal complex. This is not straightforward because histidine has two tautomeric forms, which means that the δ-and the ε-nitrogen of the imidazole possess both imine and amine character (compound 4, Scheme 5). [20] Therefore, mixtures of regioisomers are obtained when the imidazole is reacted with one equivalent of an electrophile. To obtain the desired dissymmetrically substituted histidinium salts, we applied a route based on the report by Hodges and Chivikas, [17] and was improved by Brégeon et al. [30] (Scheme 4). Scheme 4. The cyclic urea route toward dissymmetrically substituted histidinium salts.This cyclic urea route induces regioselectivity because only the six-membered cyclic urea 5 can be formed. The second nitrogen atom can then be functionalized selectively through nucleophilic substitution. Subsequently, the R 1functionalized urea compounds can be ring-opened by reaction with an alcohol, which liberates the δ-nitrogen atom of the imidazole, and provides a carbamate-protected amine. The use of tBuOH affords the Boc-protected histidine, Eur. J. Inorg. Chem. 2015, 982-996

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Allylpalladium(II) Histidylidene Complexes and Their Application in Z‐Selective Transfer Semihydrogenation of Alkynes

et al. 2015

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“…These reactions were all performed using HATU as the coupling agent according to a 70 modified literature procedure. 15 Other standard and less costly agents such as DCC 16 or N-mesyl-benzotriazole 17 were also evaluated, though these methods failed to give the desired peptide bond. According to route A (Scheme 1), the free amine 2 was reacted with commercially available Boc-L-alanine to give the Alternatively, the oligopeptide tether can be synthesised first (route B).…”

Section: Synthesis Of Alanine-based Histidylidene Metal Complexesmentioning

confidence: 99%

“…This activity corresponds to an approximately four-fold increase of turnover rates, which is presumably not only induced by the cationic nature of the rhodium centre, but also by the beneficial effect of methionine coordination. Since tyrosine chelation was not 15 detected, similar effects due to intramolecular stabilisation of the metal centre are absent with complex 11. These results underline the relevance of chelation and indicate the unique behaviour of the methionine-containing catalyst.…”

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confidence: 94%

Peptide-tethered monodentate and chelating histidylidene metal complexes: synthesis and application in catalytic hydrosilylation

2013

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“…[21] More recently, (S)-histidine has been used as a chiral precursor for a novel family of chiral amino acid and peptidic ILs. [22] On the other hand, thiazolinium-based chiral ILs have been prepared with amino alcohols as the chiral material. Gaumond and co-workers have synthesized [23] these new ILs in four steps starting from (R)-2-aminobutan-1-ol or -phenylalaninol, in fairly good overall yield (60-68 %).…”

Section: Natural Products As Sources Of the Cation Side Of Room-tempementioning

confidence: 99%

Ionic Green Solvents from Renewable Resources

2007

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Nature provides a vast new vista of opportunities for the preparation of new recyclable solvents. Natural compounds have been recently used to prepare the cationic or anionic moiety of room‐temperature ionic liquids. In many cases, these new solvents, based on modifications of natural products, contain chiral centres and/or specific functional groups. This paper is an overview in an area of research that is destined for rapid development and expansion. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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(S)-Histidine: the ideal precursor for a novel family of chiral aminoacid and peptidic ionic liquids

Cited by 45 publications

References 15 publications

Allylpalladium(II) Histidylidene Complexes and Their Application in Z‐Selective Transfer Semihydrogenation of Alkynes

Allylpalladium(II) Histidylidene Complexes and Their Application in Z‐Selective Transfer Semihydrogenation of Alkynes

Peptide-tethered monodentate and chelating histidylidene metal complexes: synthesis and application in catalytic hydrosilylation

Ionic Green Solvents from Renewable Resources

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