Sugar amino acids at the anomeric position of carbohydrates: synthesis of spirocyclic amino acids of 6-deoxy-l-lyxofuranose

Two anomeric spirodiketopiperazines and one spirohydantoin of 6-deoxy-l-lyxofuranose have been prepared from l-fucono-δ-lactone via ring contraction to the corresponding tetrahydrofuran carboxylate and anomeric functionalization including regioselective bromination and azide displacement.

The anomeric spirodiketopiperazines and spirohydantoin of 6-deoxy-l-lyxofuranose have been prepared from l-fucose.Figure optionsDownload as PowerPoint slide

2-Trifluoromethanesulfonyl-3,4-O-isopropylidene-l-fucono-1,5-lactoneC10H13F3O7S[α]D22=-64.3 (c 1.11, CHCl3)Source of chirality: l-fucose

Methyl 2,5-anhydro-6-deoxy-3,4-O-isopropylidene-l-talonateC12H22O5[α]D22=-33.8 (c 1.95, CHCl3)Source of chirality: l-fucose

Methyl 2,5-anhydro-2-bromo-6-deoxy-3,4-O-isopropylidene-l-galactonateC10H15BrO5[α]D22=-199 (c 1.60, CHCl3)Source of chirality: l-fucose

Methyl 2,5-anhydro-2-azido-6-deoxy-3,4-O-isopropylidene-l-talonateC10H15N3O5[α]D22=-35.3 (c 1.23, CHCl3)Source of chirality: l-fucose

3,4-O-Isopropylidene-l-talono-1,5-lactoneC9H14O5[α]D22=-105.4 (c 0.74, CHCl3)Source of chirality: l-fucose

2-Trifluoromethanesulfonyl-3,4-O-isopropylidene-l-talono-1,5-lactoneC10H13F3O7S[α]D22=-56.9 (c 0.91, CHCl3)Source of chirality: l-fucose

Methyl 2,5-anhydro-6-deoxy-3,4-O-isopropylidene-l-galactonateC10H16O5[α]D22=-53.9 (c 1.21, CHCl3)Source of chirality: l-fucose

Methyl 2-amino-2,5-anhydro-6-deoxy-3,4-O-isopropylidene-l-galactonateC10H17NO5[α]D23=-27.7 (c 0.95, CHCl3)Source of chirality: l-fucose

Methyl N-2-(benzyloxycarbonylglycylamino)-2,5-anhydro-3,4-O-isopropylidene-6-deoxy-l-talonateC20H26N2O8[α]D22=-3.2 (c 1.19, CHCl3)Source of chirality: l-fucose

Methyl N-2-(benzyloxycarbonylglycylamino)-2,5-anhydro-3,4-O-isopropylidene-6-deoxy-l-galactonateC20H26N2O8[α]D22=-49 (c 0.42, CHCl3)Source of chirality: l-fucose

(2S,3R,4R,5R)-3,4-O-Isopropylidene-2-methyl-6,9-diaza-1-oxaspiro-[4.5]-decane-7,10-dioneC11H16N2O5[α]D22=-56.1 (c 0.51, CHCl3)Source of chirality: l-fucose

(2S,3R,4R,5S)-3,4-O-Isopropylidene-2-methyl-6,9-diaza-1-oxaspiro-[4.5]-decane-7,10-dioneC11H16N2O5[α]D22=-152.1 (c 0.61, CH3OH)Source of chirality: l-fucose

(2S,3R,4R,5R)-3,4-O-Isopropylidene-2-methyl-6,8-diaza-1-oxaspiro-[4.4]-nonane-7,9-dioneC10H14N2O5[α]D22=-72.6 (c 0.58, CHCl3)Source of chirality: l-fucose

(2S,3R,4R,5R)-2-Methyl-6,9-diaza-1-oxaspiro-[4.5]-decane-7,10-dioneC10H18N2O5[α]D22=-1.1 (c 0.43, CH3OH)Source of chirality: l-fucose

(2S,3R,4R,5S)-2-Methyl-6,9-diaza-1-oxaspiro-[4.5]-decane-7,10-dioneC10H18N2O5[α]D22=-0.3 (c 0.41, CH3OH)Source of chirality: l-fucose

(2S,3R,4R,5R)-2-Methyl-6,8-diaza-1-oxaspiro-[4.4]-nonane-7,9-dioneC7H10N2O5[α]D22=-23.2 (c 0.57, CH3OH)Source of chirality: l-fucose