Nitroxides. IX. Synthesis of nitroxide free radical α-amino acids

Lex, L.; Hideg, Kálmán; Hankovszky, H. O.

doi:10.1139/v82-210

Cited by 12 publications

(10 citation statements)

References 6 publications

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“…A new trend with increasing significance is the nonsense suppression technology to build in unnatural amino acids [103,104]. For ESR studies of proteins, a variety of paramagnetic α-amino acids (TOAC) (89) [105], (90) [106], (91) [53]; β-amino-acids (92) (POAC) [105], 93 (β-TOAC) [107] as well as γ-amino acid 94 [48] have been synthesized. In several cases, naturally occurring amino acids were modified by alkylation or acylation with functionalized nitroxides to obtain a paramagnetic protein building block [108].…”

Section: Synthesis Of Paramagnetic Amino Acidsmentioning

confidence: 99%

Recent results in chemistry and biology of nitroxides

Hideg

Kálai

Sár

2005

Journal of Heterocyclic Chemistry

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Section: Synthesis Of Paramagnetic Amino Acidsmentioning

confidence: 99%

Recent results in chemistry and biology of nitroxides

Hideg

Kálai

Sár

2005

Journal of Heterocyclic Chemistry

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“…The synthesis of a pyrroline a-amino acid (10) in our laboratory has been described earlier (6). Two reviews deal with synthesis and spin-labelling of a-amino acids and peptides (7,8).…”

Section: Resultsmentioning

confidence: 99%

“…wt. 182.3): C 65.90,H 8.85,N 7.69;found: C 66.01,H 8.88,6, .v~rlfi)ntrt~ ( 6 ) To a stirrcd solution of 4 (2.764 g. 15 rnmol) and TEA (1.670 g, 16.5 mmol) in dichloromcthanc (25 11iL) at -10°C, mcthancsulfonyl chloridc ( I ,890 g. 16.5 mrnol) was addcd dropwisc. and stirrcd for 3 h at room tcmpcraturc.…”

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confidence: 94%

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Synthesis of novel, highly reactive 1-oxyl-2,2,6,6-tetramethyl-1,2,5,6-tetrahydropyridine derivatives

Csekö¹,

Hankovszky²,

Hideg³

1985

Can. J. Chem.

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New multipurpose spin labels and synthons can be synthesizcd from I-oxyl-2,2,6,6-tetramethyl-l,2,5,6-tetrahydropyridine-4-carboxylic acid (1). Either 1, its pentafluorophenylester (2). or acylcarbonate (3) (prepared from 1 with ethyl chloroformatc) can be reduced to I-oxyl-2,2,6,6-tetramethyl-4-hydroxymeth I ,2,5,6-tetrahydropyridine (4). The methanesulfonate (6) and the bromo compound (7) are highly reactivc alkylating reagents due, in large part, to the allylic linkage in the nitroxide ring. Thc latter can be reacted with KSS02CH1 to givc methanethiolsulfonate (9). A novel side chain spin-labelled a-amino acid ester (11) is made by a phase-transfer alkylation of a Schiff basc with 7. Compound 11 can be coupled with the protected L-phenylalanine in the presencc of dicyclohcxylcarbodiimide (DCC) to producc the nitroxide dipeptide (12).JOZSEF CSEKO, H. OLGA HANKOVSZKY et KALMAN HIDEG. Can. J . Chem. 63, 940 (1985).On peut synthttiser de nouveaux synthons et de nouveaux marqueurs de spin a usage multiple ii partir de I'acide oxyl-l tCtramCthyl-2,2,6,6 tttrahydro-I ,2,5.6 pyridinecarboxylique-4 (1). On peut rkduire soit le composC 1, soit son ester pentafluorophCnyle (2) ou son acylcarbonate (3) (que I'on peut prkparer ii partir de 1 par reaction avcc Ic chloroformate d'Cthyle) en oxyl-l tdtramCthy1-2,2,6,6 hydroxyrndthyl-4 tCtrahydro-1,2,5.6 pyridinc (4). Le mCthanesulfonate (6) ainsi que le dCrivC bromC (7) sont des reactifs alkylants trks rkactifs ii causc, en grandc partie, de la liaison allylique dans le cycle nitroxyde. On peut faire rCagir le dCrivC bromC avec le KSS02CH3 pour obtenir lc mCthanethiosulfonate 9. On a prCparC le nouvel ester 11 d'un acidc a-aminC portant un marqueur de spin sur la chaine IatCrale cn cffectuant unc alkylation par transfert de phase d'une base de Schiff par le composC 7. Dans Ic but d'obtenir le nitroxyde dipeptide (12), on peut coupler Ic composC 11 avec une L-phinylalanine en prksence dc dicyclohexylcarbodiimide (DCC).[Traduit par le journal] Introduction Reactive functional groups attached to stable nitroxide free radicals have been used as spin labels for studying biomolecules in recent decades (1). The most frequently used types of nitroxides are the pyrroline-the pyrrolidine-, and the piperidine-N-oxyls:

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“…This procedure afforded the monoalkylated product 3, which could be readily hydrolysed under acidic conditions to the corresponding amine 25 4, without affecting the N-oxyl radical moiety. The treatment of DL-amino acid esters with t-butoxycarbonyl anhydride in THF gave the corresponding protected N-Boc amino acid ethyl esters 5, which can be hydrolysed 20 to amino acid 6 ready for use in SPPS (Scheme 2).…”

Section: Chemical Synthesis Of Spin-labelled Amino Acidsmentioning

confidence: 99%

Incorporation of spin-labelled amino acids into proteins

et al. 2005

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The elucidation of structure and function of proteins and membrane proteins by EPR spectroscopy has become increasingly important in recent years as technological advances have been made in the design of spectrometers and in the chemistry of the nitroxide group. These new developments have increased the demand for tailor-made amino acids carrying a spin label on the one hand and for reliable methods for their incorporation into proteins on the other. Here we describe methods for site-specific spin labelling of proteins. It is shown that a combination of recombinant synthesis of proteins with chemically produced peptides (expressed protein ligation) allows the preparation of site-specifically spin-labelled proteins.

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Nitroxides. IX. Synthesis of nitroxide free radical α-amino acids

Abstract: Three methods are described for preparation of a new stable nitroxide free radical amino acid, 2-amino-3-(1-oxyl-2,2,5,5-tetramethyl-3-pyrrolin-3-yl) propionic acid and its derivates. This amino acid may be used as a paramagnetic amino acid synthon in studies of peptides.

Cited by 12 publications

References 6 publications

Recent results in chemistry and biology of nitroxides

Recent results in chemistry and biology of nitroxides

Synthesis of novel, highly reactive 1-oxyl-2,2,6,6-tetramethyl-1,2,5,6-tetrahydropyridine derivatives

Incorporation of spin-labelled amino acids into proteins

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