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Closed Access item Fragmentation of carbohydrate anomeric alkoxy radicals. A new general method for the synthesis of alduronic acid lactones

Authors:Francisco, Cosme G.
González Martín, Concepción C.
Suárez, Ernesto
Issue Date:17-Mar-1998
Publisher:American Chemical Society
Citation:Journal of Organic Chemistry 63(7): 2099-2109 (1998)
Abstract:Alduronic acid 4,1-, 5,1-, and 5,2-lactones can be specifically obtained when hexuronic and penturonic acids belonging to the erythrose and threose carbohydrate series undergo a tandem β-fragmentation−intramolecular cyclization reaction. In this way, γ-lactones such as 3-O-formyl-1,2-O-isopropylidene-d-threurono-4,1-lactone (38), 3-O-formyl-1,2-di-O-methyl-d-threurono-4,1-lactones (39), or 3-O-formyl-1,2-O-isopropylidene-d-erythrurono-4,1-lactone (41), and δ-lactones such as 1-O-(tert-butyldimethylsilyl)-4-O-formyl-2,3-O-isopropylidene-d-lyxurono-5,1-lactones (40), or 4-O-formyl-1,2,3-tri-O-methyl-d-arabinurono-5,1-lactones (42), or 3-O-benzyl-4-O-formyl-1,2-O-isopropylidene-d-arabinurono-5,1-lactone (43), were obtained. Alternatively, an intermolecular reaction took place when the carboxyl group was lactonized. Thus, 1,4-di-O-acetyl-3-formyl-1-iodo-d-arabinurono-5,2-lactone (45) was prepared from 2,5-di-O-acetyl-d-glucurono-6,3-lactone (37). The reaction is promoted by two different systems: (diacetoxyiodo)benzene (DIB)−iodine, under mild conditions, or diphenylhydroxyselenium acetate (DHSA)−iodine under visible light irradiation. With this new strategy, nor-aldopyranosuronic and aldofuranosuronic acid lactones are formed via 1,5 and 1,6 intramolecular cyclization.
Description:11 pages, 2 tables, 7 schemes.
Publisher version (URL):http://dx.doi.org/10.1021/jo971323p
URI:http://hdl.handle.net/10261/17257
ISSN:0022-3263
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Appears in Collections:(IPNA) Artículos

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