Synthesis of (+)-sucrose via β-d-psicofuranosylation

Despite the difficulty of direct β-furanosylation with d-fructose, the synthesis of β-d-fructofuranosyl α-d-glucopyranoside, (+)-sucrose 1, has been achieved stepwise, via β-selective d-psicofuranosylation followed by stereo inversion of a hydroxy group at the C-3 position on the furanose ring. d-Psicofuranosyl donor 10 was prepared in eight steps from d-ribose monoacetonide 3 in excellent yield.

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(2R,3S,4S)-2-Hydroxy-3,4-O-isopropylidene-hex-5-enyl benzoateC16H20O5Ee >99%[α]D = +13.2 (c 0.98, CHCl3)Source of chirality: d-riboseAbsolute configuration: (2R,3S,4S)

(2R,3S,4S)-2-tert-Butyldimethylsilyloxy-3,4-O-isopropylidene-hex-5-enyl benzoateC22H34O5SiEe >99%[α]D = −2.3 (c 1.03, CHCl3)Source of chirality: d-riboseAbsolute configuration: (2R,3S,4S)

1,6-Di-O-benzoyl-5-O-tert-butyldimethylsilyl-3,4-O-isopropylidene-d-psicoseC29H38O8SiEe >99%[α]D = +21.0 (c 1.05, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3R,4S,5R)

(1,6-Di-O-benzoyl-3,4-O-isopropylidene-β-d-psicofuranosyl) benzyl phthalateC38H34O11Ee >99%[α]D = −11.1 (c 0.89, CHCl3)Source of chirality: d-riboseAbsolute configuration: (2R,3R,4S,5R)

(1,6-Di-O-benzoyl-3,4-O-isopropylidene-α-d-psicofuranosyl) benzyl phthalateC38H34O11Ee >99%[α]D = +6.5 (c 1.06, CHCl3)Source of chirality: d-riboseAbsolute configuration: (2S,3R,4S,5R)

(1,6-Di-O-benzoyl-3,4-O-isopropylidene-β-d-psicofuranosyl) 2,3,4,6-tetra-O-benzyl-α-d-glucopyranosideC57H58O13Ee >99%[α]D = +29.0 (c 1.08, CHCl3)Source of chirality: d-ribose, d-glucoseAbsolute configuration: (2′S,3′R,4′R,5′R,1S,2R,3S,4R,5R)

(1,6-Di-O-benzoyl-3,4-O-isopropylidene-β-d-psicofuranosyl) 2,3,4,6-tetra-O-benzyl-β-d-glucopyranosideC57H58O13Ee >99%[α]D = −13.8 (c 1.00, CHCl3)Source of chirality: d-ribose, d-glucoseAbsolute configuration: (2′S,3′R,4′R,5′R,1R,2R,3S,4R,5R)

(1,6-Di-O-benzoyl-b-d-psicofuranosyl) 2,3,4,6-tetra-O-benzyl-α-d-glucopyranosideC54H54O13Ee >99%[α]D = +55.5 (c 1.03, CHCl3)Source of chirality: d-ribose, d-glucoseAbsolute configuration: (2′S,3′R,4′S,5′R,1R,2R,3S,4R,5R)

(1,3,6-Tri-O-benzoyl-β-d-psicofuranosyl) 2,3,4,6-tetra-O-benzyl-α-d-glucopyranosideC61H58O14Ee >99%[α]D = +37.5 (c 0.99, CHCl3)Source of chirality: d-ribose, d-glucoseAbsolute configuration: (2′S,3′R,4′S,5′R,1R,2R,3S,4R,5R)

(1,4,6-Tri-O-benzoyl-β-d-erythro-2,3-hexodiulofuranosyl) 2,3,4,6-tetra-O-benzyl-α-d-glucopyranosideC61H56O14Ee >99%[α]D = +98.5 (c 0.68, CHCl3)Source of chirality: d-ribose, d-glucoseAbsolute configuration: (2′S,4′R,5′R,1R,2R,3S,4R,5R)

(1,4,6-Tri-O-benzoyl-β-d-fructofuranosyl) 2,3,4,6-tetra-O-benzyl-α-d-glucopyranosideC61H58O14Ee >99%[α]D = +39.2 (c 1.00, CHCl3)Source of chirality: d-ribose, d-glucoseAbsolute configuration: (2′S,3′S,4′S,5′R,1R,2R,3S,4R,5R)