A common synthetic approach for seven and eight-membered polyhydroxylated iminocyclitols

A common strategy for making seven and eight-membered polyhydroxy iminoalditols has been developed from d-1,5-gluconolactone, using an RCM protocol as the key step.

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Benzyl allyl((R)-2-(benzyloxy)-1-((4S,4′R,5R)-2,2,2′,2′-tetramethyl-4,4′-bi(1,3-dioxolan)-5-yl)ethyl)carbamateC30H39NO7[α]D25=+21.3 (c 6.38, CHCl3)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (4S,4′R,5R)

Benzyl allyl((R)-2-(benzyloxy)-1-((4R,5R)-5-((R)-1,2-dihydroxyethyl)-2,2-dimethyl-1,3-dioxolan-4-yl)ethyl)carbamateC27H35 N O7[α]D25=+26.2 (c 4.65, CHCl3)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (4R,5R)

Benzyl allyl((R)-2-(benzyloxy)-1-((4R,5R)-2,2-dimethyl-5-vinyl-1,3-dioxolan-4-yl)et-hyl)carbamateC27H33NO5[α]D25=+18.9 (c 3.09, CHCl3)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (4R,5R)

(3aR,4R,8aR)-Benzyl 4-(benzyloxymethyl)-2,2-dimethyl-6,8a-dihydro-3aH-[1,3]diox-olo[4,5-c]azepine-5(4H)-carboxylateC25H29NO5[α]D25=-84.8 (c 2.80, CHCl3)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (3aR,4R,8aR)

(3aR,4R,7S,8S,8aR)-Benzyl 4-((benzyloxy)methyl)-7,8-dihydroxy-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]azepine-5(4H)-carboxylateC25H31NO7[α]D26=-43.1 (c 2.83, CHCl3)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (3aR,4R,7S,8S,8aR)

(3aR,4R,7R,8R,8aR)-Benzyl 4-((benzyloxy)methyl)-7,8-dihydroxy-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]azepine-5(4H)-carboxylateC25H31NO7[α]D26=-21.3 (c 3.57, CHCl3)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (3aR,4R,7R,8R,8aR)

(2R,3R,4R)-2-(Hydroxymethyl)-2,3,4,7-tetrahydro-1H-azepine-3,4-diolC7H15NO3[α]D26=+5.5 (c 1.84, MeOH)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (2R,3R,4R)

(2R,3R,4S,5S,6S)-2-(Hydroxymethyl)azepane-3,4,5,6-tetraolC7H15N O5[α]D26=+37.2 (c 1.3, MeOH)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (2R,3R,4S,5S,6S)

(2R,3R,4S,5R,6R)-2-(Hydroxymethyl)azepane-3,4,5,6-tetraolC7H15N O5[α]D26=-9.4 (c 1.28, MeOH)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (2R,3R,4S,5R,6R)

(5S,6R,7R,8R,Z)-Benzyl 8-((benzyloxy)methyl)-5,6,7-trihydroxy-5,6,7,8-tetrahydro-azocine-1(2H)-carboxylateC26H31NO6[α]D26=-83.2 (c 1.47, CHCl3)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (5S,6R,7R,8R,Z)

(5R,6R,7R,8R,Z)-Benzyl 8-((benzyloxy)methyl)-5,6,7-trihydroxy-5,6,7,8-tetrahydro-azocine-1(2H)-carboxylateC26H31NO6[α]D26=-44.4 (c 1.28, CHCl3)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (5R,6R,7R,8R,Z)

(2R,3R,4R,5S)-2-(Hydroxymethyl)azocane-3,4,5-triolC8H17N O4[α]D26=+9.6 (c   0.85, MeOH), [α]D26=+8.7 (c 0.80, H2O)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (2R,3R,4R,5S)

(2S,3R,4R,5S)-2-(Hydroxymethyl)azocane-3,4,5-triolC8H17N O4[α]D26=-4.3 (c 0.43, MeOH)Source of chirality: d-1,5-gluconolactoneAbsolute configuration: (2S,3R,4S,5R,6R)