ChemInform Abstract: Synthesis of Spiro[1,4‐benzothiazine‐2,2′‐pyrans] Starting from Methyl β‐D‐arabino‐2‐Hexulopyranosonate.

Andersch, Jens; Sicker, Dieter; Wilde, H.

doi:10.1002/chin.199937168

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“…22 Anomeric spiroketals of pyranoid sugar derivatives in which additional heteroatoms, especially nitrogen, can be found in a six-membered ring are scarcely known. Syntheses of glycopyranosylidene spiro derivatives of 1,2-oxazines, 23 1,3-oxazinones, 24 1,4-oxazines, 25 1,4-oxazinones, 26−30 nones 31 have been reported; however, their biological activity is practically unexplored so far. Only weak glycosidase inhibition and cytotoxicity for some 1,3-oxazinone derivatives have been reported.…”

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confidence: 99%

Glucopyranosylidene-spiro-benzo[b][1,4]oxazinones and -benzo[b][1,4]thiazinones: Synthesis and Investigation of Their Effects on Glycogen Phosphorylase and Plant Growth Inhibition

Kun

Kánya

Galó

et al. 2019

J. Agric. Food Chem.

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Glucopyranosylidene-spiro-benzo[b][1,4]oxazinones were obtained via the corresponding 2-nitrophenyl glycosides obtained by two methods: (a) AgOTf-promoted glycosylation of 2-nitrophenol derivatives by O-perbenzoylated methyl (α-d-gluculopyranosyl bromide)heptonate or (b) Mitsunobu-type reactions of O-perbenzoylated methyl (α-d-gluculopyranose)heptonate with bulky 2-nitrophenols in the presence of diethyl azodicarboxylate (DEAD) and PPh3. Catalytic hydrogenation (H2–Pd/C) or partial reduction (e.g., H2–Pd/C, pyridine) of the 2-nitro groups led to spiro-benzo[b][1,4]oxazinones and spiro-benzo[b][1,4]-4-hydroxyoxazinones by spontaneous ring closure of the intermediate 2-aminophenyl or 2-hydroxylamino glycosides, respectively. The analogous 2-aminophenyl thioglycosides, prepared by reactions of O-perbenzoylated methyl (α-d-gluculopyranosyl bromide)heptonate with 2-aminothiophenols, were cyclized in m-xylene at reflux temperature to the corresponding spiro-benzo[b][1,4]thiazinones. O-Debenzoylation was effected by Zemplén transesterification in both series. Spiro-configurations were determined by NMR and electronic circular dichroism time-dependent density functional theory (ECD-TDDFT) methods. Inhibition assays with rabbit muscle glycogen phosphorylase b showed (1′R)-spiro{1′,5′-anhydro-d-glucitol-1′,2-benzo[b][1,4]oxazin-3(4H)-one} and (1′R)-spiro{1′,5′-anhydro-d-glucitol-1′,2-benzo[b][1,4]thiazin-3(4H)-one} to be the most efficient inhibitors (27 and 28% inhibition at 625 μM, respectively). Plant growth tests with white mustard and garden cress indicated no effect except for (1′R)-4-hydroxyspiro{1′,5′-anhydro-d-glucitol-1′,2-benzo[b][1,4]oxazin-3(4H)-one} with the latter plant to show modest inhibition of germination (95% relative to control).

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