Electronic and steric effects on the rate of the traceless Staudinger ligation

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Electronic and steric effects on the rate of the traceless Staudinger ligation.

Interplay between electronic effects imparted by phosphinothiol substituents and steric effects imposed by amino-acid reactants affects the rate of the traceless Staudinger ligation of peptides in a predictable manner.

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Coulombic effects on the traceless Staudinger ligation in water.

The traceless Staudinger ligation can be mediated by phosphinothiols under physiological conditions. Proximal positive charges are necessary to achieve that transformation, presumably because those charges discourage protonation of the key iminophosphorane intermediate. Here, a series of cationic phosphinothiols is used to probe Coulombic effects on the traceless Staudinger ligation in aqueous ...

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Protein engineering with the traceless Staudinger ligation.

The engineering of proteins can illuminate their biological function and improve their performance in a variety of applications. Within the past decade, methods have been developed that facilitate the ability of chemists to manipulate proteins in a controlled manner. Here, we present the traceless Staudinger ligation as a strategy for the convergent chemical synthesis of proteins. This reaction...

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Reaction mechanism and kinetics of the traceless Staudinger ligation.

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. Experiments with [(18)O]H(2)O indicated that the reaction mediated by (diphenylphosphino)methanethiol proceeded by S-->N acyl transfer of th...

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ژورنال

عنوان ژورنال: Organic & Biomolecular Chemistry

سال: 2008

ISSN: 1477-0520,1477-0539

DOI: 10.1039/b802336k