- High-yielding staudinger ligation of a phosphinothioester and azide to form a peptide
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(eqution presented) The Staudinger ligation can be used to couple a peptide with a C-terminal phosphinothioester to another with an N-terminal α-azido group to form a single peptide that contains no residual atoms. Here, diphenylphosphinomethanethiol thio
- Nilsson, Bradley L.,Kiessling, Laura L.,Raines, Ronald T.
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- Development of a Visible Light Triggerable Traceless Staudinger Ligation Reagent
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A series of substituted 9-methylenylanthracene photocages for diphenylphosphinothioesters have been synthesized to explore their photo-uncaging properties by visible light. Substituents such as phenyl, p-trifluoromethylphenyl, p-methoxyphenyl, ethyn-1-ylbenzene, and 3,3-dimethylbut-1-yn-1-yl have been introduced in order to extend the π-conjugation of the photocage and to shift the wavelength response of the uncaging process to the visible spectral range. Among these new photocages, the (10-(3,3-dimethylbut-1-yn-1-yl)anthracen-9-yl)methyl has been shown to have the best performance in terms of fast photo-uncaging and minimal byproduct formation. It is responsive to both UV and visible photoexcitation. Quantum yields of the photoinduced heterolytic anthracenylmethyl-phosphorus bond cleavage at 366 and 416 nm were found to be 0.08 and 0.025, respectively. This photocage enables traceless Staudinger ligation to be triggered by photoirradiation in the visible spectral range for bioconjugation applications. We demonstrate this with a series of visible-light-induced oligopeptide syntheses via the conjugation of amino acid/oligopeptide building blocks by the characteristic peptide linkage attained by traceless Staudinger ligation. Yields of the resultant conjugated oligopeptides ranged from 31 to 43%. This new photocage opens up the possibility of in situ synthesis of functional proteins/peptides mediated by visible-light-induced photoclick processes for the regulation of cellular/metabolic functions of life systems.
- Hu, Peng,Berning, Karsten,Lam, Yun-Wah,Ng, Isabel Hei-Ma,Yeung, Chi-Chung,Lam, Michael Hon-Wah
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p. 12998 - 13010
(2018/11/20)
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- Facile synthesis of peptide-porphyrin conjugates: Towards artificial catalase
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A facile synthetic method for peptide-porphyrin conjugates containing four peptide units on one porphyrin was developed using chemoselective reactions. The key building blocks, 5,10,15,20-tetrakis(3-azidophenyl)porphyrin 1 and 5,10,15,20-tetrakis(5-azido-3-pyridyl)porphyrin 2, were efficiently synthesized and used as substrates for two well-known chemoselective reactions, traceless Staudinger ligation and copper-catalyzed azide alkyne cycloaddition (so-called click chemistry). Both reactions gave the desired compounds, and click chemistry was superior for our purpose. To confirm the value of the established methodology, nine peptide-porphyrin conjugates were synthesized, and their catalase- and peroxidase-like activity in water was evaluated. Our synthetic strategy is expected to be valuable for the preparation of artificial heme protein models.
- Umezawa, Naoki,Matsumoto, Nobuyoshi,Iwama, Shinsuke,Kato, Nobuki,Higuchi, Tsunehiko
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experimental part
p. 6340 - 6350
(2010/10/04)
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- Reaction mechanism and kinetics of the traceless Staudinger ligation
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The traceless Staudinger ligation enables the formation of an amide bond between a phosphinothioester (or phosphinoester) and an azide without the incorporation of residual atoms. Here, the coupling of peptides by this reaction was characterized in detail
- Soellner, Matthew B.,Nilsson, Bradley L.,Raines, Ronald T.
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p. 8820 - 8828
(2007/10/03)
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- CHEMICAL SYNTHESIS OF REAGENTS FOR PEPTIDE COUPLING
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The present invention provides improved methods for synthesis of phosphinothiol reagents, as well as novel protected reagents, for use in formation of amide bonds, and particularly for peptide ligation. The invention provides phosphineborane complexes useful as reagents in the formation of amide bonds, particularly for the formation of an amide bond between any two of an amino acid, a peptide, or a protein.
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- Staudinger ligation of α-azido acids retains stereochemistry
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The Staudinger ligation of peptides with a C-terminal phosphinothioester and N-terminal azide is an emerging method in protein chemistry. Here, the first Staudinger ligations of nonglycyl azides are reported and shown to proceed both in nearly quantitative yield and with no detectable effect on the stereochemistry at the α-carbon of the azide. These results demonstrate further the potential of the Staudinger ligation as a general method for the total synthesis of proteins from peptide fragments.
- Soellner, Matthew B.,Nilsson, Bradley L.,Raines, Ronald T.
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p. 4993 - 4996
(2007/10/03)
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