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A. J. Steiner et al.
silica gel, gave the desired target compound as green, fluorescent
syrup.
4H, H-1ax, H-5ax, H-1ꢀax, H-5ꢀax), 1.90–1.30 (m, 12H, 2 × H-3
L, 2 × H-4 L, 2 × H-5 L, 2 × H-3 Lꢀ, 2 × H-4 Lꢀ, 2 × H-5 Lꢀ),
1.44 (s, 9H, BOC). δC (125 MHz, CD3OD) 174.1, 172.8 (C-1 L,
C-1 Lꢀ), 156.6 (BOC), 79.4 (BOC), 78.9, 78.9 (C-3, C-3ꢀ), 70.0,
70.0, 70.0, 70.0 (C-2, C-4, C-2ꢀ, C-4ꢀ), 58.0, 58.0, 58.0, 58.0 (C-
1, C-5, C-1ꢀ, C-5ꢀ), 57.5, 57.4 (C-6 L, C-6 Lꢀ), 54.6, 52.3 (C-2
L, C-2 Lꢀ), 51.6 (OCH3), 32.0, 31.1 (C-3 L, C-3 Lꢀ), 27.6, 27.6,
27.6 (BOC), 26.0, 25.9, 23.5, 23.4 (C-4 L, C-5 L, C-4 Lꢀ, C-5
Lꢀ). Calcd for [C28H52N4O11]: m/z 620.7470; ESI-MS found:
[M + H]+ 621.76, [M + Na]+ 643.74.
Methyl N2-(tert-Butoxycarbonyl)-N6-(1,5-dideoxyxylitol-
1,5-diyl)-L-lysinate 9
Following general procedure A, 1,2-O-isopropylidene-α-d-
glucofuranose 5 (3.00 g, 13.6 mmol) was dissolved in MeOH
(100 mL) and water (40 mL) and reacted with sodium periodate
(5.80 g, 27.1 mmol, 2.0 eq.) to give crude 6 (2.79 g, 13.5 mmol,
99%). 1,2-O-Isoproplidene-α-d-xylo-pentodialdo-1,4-furanose
6 (0.70 g, 3.4 mmol) gave crude 7 (0.55 g, 3.3 mmol, 98%).
Crude xylo-pentodialdose 7 (100 mg, 0.602 mmol, 1.2 eq.) was
reacted with 8 (195 mg, 0.49 mmol). Purification by column
chromatography (CHCl3/MeOH 7/1, containing 1% NH4OH)
gave compound 9 (128 mg, 0.34 mmol, 69%) as colourless
syrup. [α]D −10.6◦ (c 2.1, MeOH). δH (500 MHz, CD3OD) 4.09
(m, 1H, H-2 L), 3.71 (s, 3H, OCH3), 3.49 (m, 2H, H-2, H-4),
3.09 (t, 1H, J2,3 = J3,4 8.8, H-3), 2.96 (dd, 2H, J1eq,2 = J4,5eq 4.4,
J1eq,1ax = J5eq,5ax 10.7, H-1eq, H-5eq), 2.39 (t, 2H, 2 × H-6 L),
1.90 (dd, 2H, J1ax,2 = J4,5ax 10.7, H-1ax, H-5ax), 1.82–1.34 (m,
6H, 2 × H-3 L, 2 × H-4 L, 2 × H-5 L), 1.44 (s, 9H, BOC). δC
(125 MHz, CD3OD) 173.8 (C-1 L), 157.0 (BOC), 79.4 (BOC),
79.3 (C-3), 70.2, 70.2 (C-2, C-4), 58.3, 58.3 (C-1, C-5), 57.4 (C-
6 L), 53.8 (C-2 L), 51.5 (OCH3), 31.3 (C-3 L), 27.6, 27.6, 27.6
(BOC), 26.1, 23.6 (C-4 L, C-5 L). MS: Calcd for [C17H32N2O7]:
m/z 376.4599; ESI-MS found: [M + H]+ 377.47, [M + Na]+
399.45.
Methyl N2-(Dansyl)-N6-(1,5-dideoxyxylitol-1,5-diyl)-
L-lysinate 9a
GeneralprocedureBappliedoncompound 9(66 mg, 0.18 mmol)
gave, after purification by column chromatography on silica
gel (CHCl3/MeOH 7/1, containing 1% NH4OH), compound 9a
(46 mg, 0.090 mmol, 51%) as green syrup. [α]D +3.3◦ (c 2.1,
MeOH). δH (500 MHz, CD3OD) 8.56 (d, 1H, dansyl), 8.38 (d,
1H, dansyl), 8.18 (d, 1H, dansyl), 7.59 (t, 1H, dansyl), 7.55 (t,
1H, dansyl), 7.27 (d, 1H, dansyl), 3.72 (m, 1H, H-2 L), 3.44
(m, 2H, H-2, H-4), 3.22 (s, 3H, OCH3), 3.06 (t, 1H, J2,3 = J3,4
8.8, H-3), 2.87 (s, 6H, dansyl), 2.82 (dd, 2H, J1eq,2 = J4,5eq 4.4,
J1eq,1ax = J5eq,5ax 10.7, H-1eq, H-5eq), 2.03 (m, 2H, 2 × H-6 L),
1.80 (dd, 1H, J1ax,2 or J4,5ax 10.3, H-1ax or H-5ax), 1.78 (dd,
1H, J1ax,2 or J4,5ax 10.3, H-1ax or H-5ax), 1.54 (m, 2H, 2 × H-
3 L), 1.22–0.96 (m, 4H, 2 × H-4 L, 2 × H-5 L). δC (125 MHz,
CD3OD) 172.5 (C-1 L), 152.0, 135.8, 130.3, 129.9, 129.9, 129.4,
127.9, 123.1, 119.7, 115.2 (dansyl), 79.3 (C-3), 70.2, 70.2 (C-2,
C-4), 58.3, 58.1 (C-1, C-5), 57.2 (C-6 L), 55.8 (C-2 L), 51.2
(OCH3), 44.7, 44.7 (dansyl), 31.9 (C-3 L), 25.4, 23.0 (C-4 L, C-
5 L). Calcd for [C24H35N3O7S]: m/z 509.6356; ESI-MS found:
[M + H]+ 510.70, [M + Na]+ 532.63.
Methyl 6-{[N2-(tert-Butoxycarbonyl)-N6-(1,5-
dideoxyxylitol-1,5-diyl)-L-lysyl]amino}hexanoate 11
Following general procedure A, xylo-pentodialdose 7 (60 mg,
0.36 mmol) was reacted with compound 10 (184 mg, 0.36 mmol,
1.0 eq.). Purification by column chromatography on silica
gel (CHCl3/MeOH 7/1, containing 1% NH4OH), yielded 11
(129 mg, 0.263 mmol, 73%) as colourless syrup. [α]D −6.6◦
(c 1.8, MeOH). δH (500 MHz, CD3OD) 3.95 (m, 1H, H-2 L),
3.65 (s, 3H, OCH3), 3.48 (m, 2H, H-2, H-4), 3.25–3.12 (m,
2H, 2 × H-6C), 3.08 (t, 1H, J2,3 = J3,4 9.0, H-3), 2.96 (dd,
2H, J1eq,2 = J4,5eq 4.9, J1eq,1ax = J5eq,5ax 11.2, H-1eq, H-5eq),
2.39 (t, 2H, 2 × H-6 L), 2.32 (t, 2H, 2 × H-2C), 1.90 (dd, 2H,
J1ax,2 = J4,5ax 10.7, H-1ax, H-5ax), 1.75–1.30 (m, 12H, 2 × H-
3C, 2 × H-4C, 2 × H-5C, 2 × H-3 L, 2 × H-4 L, 2 × H-5 L), 1.44
(s, 9H, BOC). δC (125 MHz, CD3OD) 174.6, 174.0 (C-1C, C-
1 L), 156.6 (BOC), 79.4 (BOC), 79.4 (C-3), 70.2, 70.2 (C-2,
C-4), 58.3, 58.3 (C-1, C-5), 57.5 (C-6 L), 55.0 (C-2 L), 50.9
(OCH3), 38.9 (C-6C), 33.5 (C-2C), 32.2 (C-3 L), 28.9 (C-5C),
27.6, 27.6, 27.6 (BOC), 26.2, 26.2, 24.5, 23.7 (C-3C, C-4C, C-
4 L, C-5 L). Calcd for [C23H43N3O8]: m/z 489.6146; ESI-MS
found: [M + H]+ 490.62, [M + Na]+ 512.60.
Methyl 6-{[N2-(Dansyl)-N6-(1,5-dideoxyxylitol-1,5-diyl)-
L-lysyl]amino}hexanoate 11a
General procedure B applied on compound 11 (88 mg,
0.18 mmol) gave, after purification by column chromatogra-
phy on silica gel (CHCl3/MeOH 5/1, containing 1% NH4OH),
compound 11a (65 mg, 0.10 mmol, 58%) as green syrup. [α]D
−13.6◦ (c 1.1, MeOH). δH (500 MHz, CD3OD) 8.56 (d, 1H,
dansyl), 8.38 (d, 1H, dansyl), 8.21 (d, 1H, dansyl), 7.61 (t, 1H,
dansyl), 7.57 (t, 1H, dansyl), 7.28 (d, 1H, dansyl), 3.65 (s, 3H,
OCH3), 3.56 (m, 1H, H-2 L), 3.43 (m, 2H, H-2, H-4), 3.05 (t, 1H,
J2,3 = J3,4 8.8, H-3), 2.88 (s, 6H, dansyl), 2.86 (m, 2H, 2 × H-
6C), 2.81 (dd, 2H, J1eq,2 = J4,5eq 4.9, J1eq,1ax = J5eq,5ax 11.2,
H-1eq, H-5eq), 2.27 (t, 2H, 2 × H-2C), 1.97 (m, 2H, 2 × H-6 L),
1.78 (dd, 1H, J1ax,2 or J4,5ax 10.7, H-1ax or H-5ax), 1.76 (dd, 1H,
J1ax,2 or J4,5ax 10.7, H-1ax or H-5ax), 1.56–0.82 (m, 12H, 2 × H-
3C, 2 × H-4C, 2 × H-5C, 2 × H-3 L, 2 × H-4 L, 2 × H-5 L). δC
(125 MHz, CD3OD) 174.6, 172.7 (C-1C, C-1 L), 152.1, 135.6,
130.4, 130.0, 129.8, 129.5, 128.1, 123.2, 119.4, 115.3 (dansyl),
79.4 (C-3), 70.2, 70.2 (C-2, C-4), 58.4, 58.1 (C-1, C-5), 57.3,
56.9 (C-2 L, C-6 L), 50.9 (OCH3), 44.7, 44.7 (dansyl), 38.8 (C-
6C), 33.5 (C-2C), 32.5 (C-3 L), 28.5 (C-5C), 26.1, 25.6, 24.4,
23.1 (C-3C, C-4C, C-4 L, C-5 L). Calcd for [C30H46N4O8S]: m/z
622.7993;ESI-MSfound:[M + H]+ 623.81, [M + Na]+ 645.79.
Methyl N2-(tert-Butoxycarbonyl)-N6-(1,5-dideoxyxylitol-
1,5-diyl)-L-lysyl-N6-(1,5-dideoxyxylitol-1,5-diyl)-
L-lysinate 13
Following general procedure A, xylo-pentodialdose 7 (420 mg,
2.53 mmol, 3.3 eq.) was reacted with compound 12 (500 mg,
0.761 mmol). Purification by column chromatography on silica
gel (CHCl3/MeOH 2/1, containing 1% NH4OH), yielding 13
(370 mg, 0.596 mmol, 78%) as colourless syrup. [α]D −7.3◦ (c
1.6, MeOH). δH (500 MHz, CD3OD) 4.41 (m, 1H, H-2 L), 4.04
(m, 1H, H-2 Lꢀ), 3.71 (s, 3H, OCH3), 3.50 (m, 4H, H-2, H-4,
H-2ꢀ, H-4ꢀ), 3.11 (m, 2H, H-3, H-3ꢀ), 2.99 (m, 4H, H-1eq, H-5eq,
H-1ꢀeq, H-5ꢀeq), 2.44 (m, 4H, 2 × H-6 L, 2 × H-6 Lꢀ), 1.97 (m,
Methyl N2-(Dansyl)-N6-(1,5-dideoxyxylitol-1,5-diyl)-
L-lysyl-N6-(1,5-dideoxyxylitol-1,5-diyl)-L-lysinate 13
General procedure B applied on compound 13 (100 mg,
0.161 mmol) gave, after purification by column chromatography