Syntheses of l-glucosamine donors for 1,2-trans-glycosylation reactions

Two new l-glucosamine donors, that is pent-4-enyl 3,4,6-tri-O-acetyl-2-allyloxycarbonylamino-2-deoxy-β-l-glucopyranoside 16 and ethyl 3,4,6-tri-O-acetyl-2-allyloxycarbonylamino-2-deoxy-1-thio-β-l-glucopyranoside 21 were prepared in 12 steps from l-arabinose. The reaction pathway uses 3,4,6-tri-O-acetyl-l-glucal 5, and then 3,4,6-tri-O-acetyl-2-deoxy-2-iodo-α-l-mannopyranosyl azide 8 as intermediates. The latter, together with donors 16 and 21, were used for preparing l-glucosamine neoglycolipids.

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1,3,4,6-Tetra-O-acetyl-2-deoxy-2-iodo-β-l-glucopyranoseC14H19IO9[α]D21=-64.5 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1R,2S,3R,4S,5S)

1,3,4,6-Tetra-O-acetyl-2-deoxy-2-iodo-α-l-mannopyranoseC14H19IO9[α]D21=-15.0 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2R,3R,4S,5S)

3,4,6-Tri-O-acetyl-2-deoxy-2-iodo-α-l-mannopyranosyl azideC14H19IO9[α]D21=-81.8 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1R,2R,3R,4S,5S)

Cholesteryl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-l-glucopyranosideC41H65NO9[α]D21=-14.1 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4S,5S)

10-Undecyloxymethyl-3,6,9,12-tetraoxatricosyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-l-glucopyranosideC45H83NO14[α]D21=+14.5 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4S,5S)

Pent-4-enyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-l-glucopyranosideC19H29NO9[α]D21=+15.3 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4S,5S)

Pent-4-enyl N-acetyl-3,4,6-tri-O-acetyl-N-tert-butoxycarbonylamino-2-deoxy-β-l-glucopyranosideC24H37NO11[α]D21=+20.3 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4S,5S)

Pent-4-enyl N-acetyl-3,4,6-tri-O-acetyl-N-tert-butoxycarbonylamino-2-deoxy-β-d-glucopyranosideC24H37NO11[α]D21=-20.2 (c 1.0, CHCl3)Source of chirality: d-glucoseAbsolute configuration: (1R,2R,3R,4R,5R)

Pent-4-enyl 3,4,6-tri-O-acetyl-2-tert-butoxycarbonylamino-2-deoxy-β-l-glucopyranosideC22H35NO10[α]D21=+1.9 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4S,5S)

Pent-4-enyl 3,4,6-tri-O-acetyl-2-tert-butoxycarbonylamino-2-deoxy-β-d-glucopyranosideC22H35NO10[α]D21=-2.5 (c 1.0, CHCl3)Source of chirality: d-glucoseAbsolute configuration: (1R,2R,3R,4R,5R)

Pent-4-enyl 3,4,6-tri-O-acetyl-2-amino-2-deoxy-β-l-glucopyranosideC17H27NO8[α]D21=-5.1 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4S,5S)

Pent-4-enyl 3,4,6-tri-O-acetyl-2-allyloxycarbonylamino-2-deoxy-β-l-glucopyranosideC21H31NO10[α]D21=-1.0 (c 5.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4S,5S)

Ethyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-β-l-glucopyranosideC16H25NO8S[α]D21=+42.8 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1R,2S,3S,4R,5S)

Ethyl N-acetyl-3,4,6-tri-O-acetyl-2-tert-butoxycarbonylamino-2-deoxy-1-thio-β-l-glucopyranosideC21H33NO10S[α]D21=+5.7 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1R,2S,3S,4R,5S)

Ethyl N-acetyl-3,4,6-tri-O-acetyl-2-tert-butoxycarbonylamino-2-deoxy-1-thio-β-d-glucopyranosideC21H33NO10S[α]D21=-6.2 (c 1.0, CHCl3)Source of chirality: d-glucoseAbsolute configuration: (1S,2R,3R,4S,5R)

Ethyl 3,4,6-tri-O-acetyl-2-tert-butoxycarbonylamino-2-deoxy-1-thio-β-l-glucopyranosideC19H31NO9S[α]D21=+22.9 (c 1.6, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1R,2S,3S,4R,5S)

Ethyl 3,4,6-tri-O-acetyl-2-tert-butoxycarbonylamino-2-deoxy-1-thio-β-d-glucopyranosideC19H31NO9S[α]D21=-23.0 (c 1.0, CHCl3)Source of chirality: d-glucosamine, hydrochlorideAbsolute configuration: (1S,2R,3R,4S,5R)

Ethyl 3,4,6-tri-O-acetyl-2-allyloxycarbonylamino-2-deoxy-1-thio-β-l-glucopyranosideC18H27NO9S[α]D21=+18.5 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1R,2S,3S,4R,5S)

10-Tetradecyloxymethyl-3,6,9,12-tetraoxahexacosyl 3,4,6-tri-O-acetyl-2-allyloxycarbonylamino-2-deoxy-β-l-glucopyranosideC53H97NO15[α]D21=+5.6 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4S,5S)

1,3-Bis(undecyloxy)prop-2-yl 3,4,6-tri-O-acetyl-2-allyloxycarbonylamino-2-deoxy-β-l-glucopyranosideC41H73NO12[α]D21=-6.1 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4S,5S)

1,3-Bis(undecyloxy)prop-2-yl 3,4,6-tri-O-acetyl-2-allyloxycarbonylamino-2-deoxy-β-d-glucopyranosideC41H73NO12[α]D21=+6.5 (c 1.0, CHCl3)Source of chirality: d-glucosamine, hydrochlorideAbsolute configuration: (1R,2R,3R,4R,5R)

10- Tetradecyloxymethyl-3,6,9,12-tetraoxahexacosyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-l-glucopyranosideC51H95NO14[α]D21=+13.5 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4S,5S)

1,3-Bis(undecyloxy)prop-2-yl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-l-glucopyranosideC39H71NO11[α]D21=-1.0 (c 2.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4S,5S)

1,3-Bis(undecyloxy)prop-2-yl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-d-glucopyranosideC39H71NO11[α]D21=+0.8 (c 2.0, CHCl3)Source of chirality: d-glucosamine, hydrochlorideAbsolute configuration: (1R,2R,3R,4R,5R)

Cholesteryl 2-acetamido-2-deoxy-β-l-glucopyranosideC35H59NO6[α]D21=-4.3 (c 0.6, CHCl3–MeOH 4:1)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4R,5S)

10-Undecyloxymethyl-3,6,9,12-tetraoxatricosyl 2-acetamido-2-deoxy-β-l-glucopyranosideC39H77NO11[α]D21=+29.2 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4R,5S)

10-Tetradecyloxymethyl-3,6,9,12-tetraoxahexacosyl 2-acetamido-2-deoxy-β-l-glucopyranosideC45H89NO11[α]D21=+26.0 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4R,5S)

1,3-Bis(undecyloxy)prop-2-yl 2-acetamido-2-deoxy-β-l-glucopyranosideC33H65NO8[α]D21=+16.0 (c 1.0, CHCl3)Source of chirality: l-arabinoseAbsolute configuration: (1S,2S,3S,4R,5S)

1,3-Bis(undecyloxy)prop-2-yl 2-acetamido-2-deoxy-β-d-glucopyranosideC33H65NO8[α]D21=-15.9 (c 1.0, CHCl3)Source of chirality: d-glucosamine, hydrochlorideAbsolute configuration: (1R,2R,3R,4S,5R)