A novel free C-12 higher carbon sugar: asymmetric synthesis and reactivity with nucleophiles

A novel C-12 higher carbon sugar, (1R)-(1,4:3,6-dianhydro-d-mannitol-2-yl)-1,4:3,6-dianhydro-d-fructose, was firstly synthesized via a convenient aldol reaction of 1,4:3,6-dianhydro-d-fructose without any protection and activation of functional groups. The reactivity of the novel higher sugar with nucleophiles was also studied, through which a series of oxazolidines and other derivatives of the higher sugar were available. The study showed that the higher sugar possesses a highly reactive carbonyl group and a good stereo controlling ability in the reaction.

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(1R)-(1,4:3,6-Dianhydro-d-mannitol-2-yl)-1,4:3,6-dianhydro-d-fructoseC12H16O8[α]D20=+173.4 (c 1.10, CH3OH)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2′R)

(2R,3R,3aS,6R,6aR,3′R,3′aS,6′R,6′aR)-Spiro[6,3′,6′-trihydroxy-octahydro[2,3′]bi[furo[3,2-b]furan]-3,2″-[1″,3″-oxazodiline]C14H21NO8[α]D20=+105.7 (c 1.06, CH3OH)Source of chirality: asymmetric synthesisAbsolute configuration: (3R)

(1S)-(1,4:3,6-Dianhydro-d-mannitol-2-yl)-2-nitromethyl-1,4:3,6-dianhydro-d-glucitolC13H19NO10[α]D20=+92.9 (c 1.06, CH3OH)Source of chirality: asymmetric synthesisAbsolute configuration: (2R)

(2R,3R,3aS,6R,6aR,3′R,3′aS,6′R,6′aR)-Spiro[6‴-hydroxy-tetrahydro-furo[3,2-b]furan]-3‴,2-[6,4′,4″-trihydroxy-5-methoxycarbonyl-furo[2″,3″:4′,5′]furo[2,3-c]pyran-5-ene]C16H20O11[α]D20=+81.0 (c 0.218, H2O)Source of chirality: asymmetric synthesisAbsolute configuration: (3R)