A recyclable heavy fluorous tag carrying an allyl alcohol pendant group: design and evaluation toward applications in synthetic carbohydrate chemistry

• Novel heavy fluorous tags carrying an allyl alcohol group were designed and synthesized.
• The tagged glycoside suited to a series of chemical modification and glycosylation.
• Upon treatment with Pd(PPh3)4, the sugar moiety could be released from the tag.
• With the Pd-catalyzed releasing reaction, the original tag can be recovered.

Toward applications in synthetic carbohydrate chemistry, we converted our previous acid-resistant heavy fluorous tag [(Rf)3C–CH2–OH, 1] to allyl alcohol derivatives [(Rf)3C–CH2–O–(CH2)n–CHCH–CH2–OH, 3 (n=1) or 4 (n=3)] by means of olefin cross metathesis. They were then subjected to β-glycosylation reactions by using a series of glycosyl donors, including glycosyl bromide and trichloroacetimidates. The terminal OH group in 3 and 4 was found to be β-glycosylated in moderate yield when 2,3,4,6-tetra-O-benzoyl-d-galactosyl trichloroacetimidate was used as the glycosyl donor. Upon a detachment reaction using Pd(PPh3)4, the initial heavy fluorous tag 1 was recovered in high yield (>90%) together with 1-hydroxy sugar, indicating that not only the allyl ether linkage in the glycosides but also the internal di-alkyl ether linkage in 4 be cleaved by the action of the Pd-catalyst enabling long-range olefin transmigration. Potential utility was demonstrated by using the tetra-O-benzoyl-β-d-galactosylated derivative of 3 in a series of deprotection, protection and glycosylation reactions, which were conductible in high yields without using chromatographic purification process. These findings prompt us to propose a general scheme in which the acid-resistant heavy fluorous compound 1 is applied as a recyclable tag in synthetic carbohydrate chemistry.

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