An efficient and general de novo synthetic route to enantiomerically pure l-hexoses has been accomplished starting from the heterocyclic homologating agent 5,6-dihydro-1,4-dithiin-2-yl[(4-methoxybenzyl)oxy]methane and methyl α,β-isopropylidene-l-glycerate. The sugar scaffold was constructed by an acid-catalyzed domino reaction, which enabled selective preparation of either methyl 2,3-dideoxy-α-l-threo-hex-2-enopyranosides or 1,6-anhydro-2,3-dideoxy-β-l-threo-hex-2-enopyranose as key intermediates. The subsequent double bond functionalization by syn or anti dihydroxylation reactions allowed introduction of the remaining stereogenic centers, leading to desired orthogonally protected l-hexopyranosides with a high degree of diastereoselectivity and with very good overall yields. These and previous results (based on the use of the corresponding l-erythro epimers) contribute to make our approach general and place it among the few methods able to synthesize the whole series of the rare l-hexoses.
Highly Stereoselective de Novo Synthesis of l-Hexoses / Guaragna, Annalisa; D’Alonzo, D.; Paolella, Concetta; C., Napolitano; Palumbo, Giovanni. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - ELETTRONICO. - 75:11(2010), pp. 3558-3568. [10.1021/jo100077k]
Highly Stereoselective de Novo Synthesis of l-Hexoses
GUARAGNA, ANNALISA;D. D’Alonzo;PAOLELLA, CONCETTA;PALUMBO, GIOVANNI
2010
Abstract
An efficient and general de novo synthetic route to enantiomerically pure l-hexoses has been accomplished starting from the heterocyclic homologating agent 5,6-dihydro-1,4-dithiin-2-yl[(4-methoxybenzyl)oxy]methane and methyl α,β-isopropylidene-l-glycerate. The sugar scaffold was constructed by an acid-catalyzed domino reaction, which enabled selective preparation of either methyl 2,3-dideoxy-α-l-threo-hex-2-enopyranosides or 1,6-anhydro-2,3-dideoxy-β-l-threo-hex-2-enopyranose as key intermediates. The subsequent double bond functionalization by syn or anti dihydroxylation reactions allowed introduction of the remaining stereogenic centers, leading to desired orthogonally protected l-hexopyranosides with a high degree of diastereoselectivity and with very good overall yields. These and previous results (based on the use of the corresponding l-erythro epimers) contribute to make our approach general and place it among the few methods able to synthesize the whole series of the rare l-hexoses.File | Dimensione | Formato | |
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