Azides in Carbohydrate Chemistry
نویسنده
چکیده
The fi rst az.ide-contain ing sugar, a glycosyl azide. was reponed in 1930 by Bertho. j Since that lime various methods have been developed for the introduction of azides at d ifferent positions of sugars. A survey of available methods is given in Section 16.2. Unlillhc lale I 970s, azidcs contai ned in carbohydrate deri vatives were simply used as accessible syn-thons [or amities because of their easily performed red uction to amines. Due 10 their stability agai nst a variety of reaction conditions, al.ides often can serve as masked amincs during the course of carbohydrate synthesis. The development of the diazo tmnsfer reaction faci litated the use of azides a lso as temporary protecting group for amines. Thi s was extensively applied during the preparation of nrninoglycoside deri vati ves (Section 16.3). Over the lasl th ree decades, azides became un important too l especially for the synthesis of g lycopeptides and-prote ins. In 1978 Paulsen el 0/. developed the 'a1.idc method' for the preparation of I ,2-cis-glyeosides of glycosam ine deri vatives using 2-nzido-2-deoxy-donors (Section 16.4). This reaction is widely used for the synthesis of O-li nked glycosyl amino acid building blocks. In N-glycoproteins, the glycan chains are attached to the protein via a {j-glycosyl amide. Staudinger-type reactions offer a conven ient access to such structures and are applied since the 19905 for the synthesis of a-and {j-glycosyl amides directly from glycosyl azides (Section 16.5). An enormous impact o n the field of glycobiology duri ng the last decade hurl the development of two bioorlhogonal reactio ns based on uzidcs: thc coppcr-catalyzed azide-alkync 13+2J cycloudclition unci the Staudinger ligution. Togcther with the possibility of ill vivo incorpor:ltion of azidc and alkync tags into glycuns and protci ns, these reactions offcr ncw options for selective labelin8 and man ipulation of biomoleculcs even within Konstanzer Online-Publikations-System (KOPS)
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