2,2,2, trifluoroethane sulfonyl chloride
immobilized alkane thiols
Biochemistry and Biotechnology
Wiley InterScience Backfile Collection 1832-2000
A major problem in affinity technology is the analysis of the synthesized solid supports, since liquid phase methodology can generally not be applied. Recently we reported a novel reaction sequence for the 2,2,2-trifluoroethanesulfonyl chloride (tresyl chloride) coupling of nucleophiles [Demiroglou et al. (1994) Angew. Chem. Int. Ed. Engl. 33, 120-123] to agarose and concluded that previously proposed structures could not be correct. However it was not possible for us to conclusively define the new reaction products because the agarose derivatives could not be solubilized for customary liquid state 13C NMR analysis. Therefore in this paper solid state 13C CP/MAS NMR spectroscopy is applied for the first time to the polysacharide agarose. Using alkyl agarose derivatives prepared by the carbonyldiimidazol method as control we found that reliable spectra in agreement with the published reaction mechanism could be obtained. The method was then applied to the novel reaction products of the tresyl chloride reaction. From the solid state 13C NMR spectra and other quantitative data it is concluded that a β-sulfonyl carboxylic acid is generated during alkaline hydrolysis of tresyl agarose and that alkyl amines are coupled by a β-sulfonyl amide bond in an elimination-addition reaction in the absence of SO-and SC-scission of the tresyl group. In the case of alkane thiol coupling the absence of SC-scission cannot be demonstrated indicating either a different reaction mechanism or possibly a mixture of reaction products.
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