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

Kazuo Fukuda, Mami Tojino, Kohtaro Goto, Hirofumi Dohi, Yoshihiro Nishida, Mamoru Mizuno

Carbohydrate research 2015 Apr 30

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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-CH=CH-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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Citation

Kazuo Fukuda, Mami Tojino, Kohtaro Goto, Hirofumi Dohi, Yoshihiro Nishida, Mamoru Mizuno. A recyclable heavy fluorous tag carrying an allyl alcohol pendant group: design and evaluation toward applications in synthetic carbohydrate chemistry. Carbohydrate research. 2015 Apr 30;407:122-30