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70.5 (C5α), 65.0 (C6αβ). 2,6-di-O-ester: H NMR δppm: 3.51
(C6″). 6,6″-di-O-ester: 1H NMR δppm: 2.55 (αCH), 2.89
(βCH2a), 4.32 (H-1α), 3.23 (H-2α), 3.68 (H-2β), 3.33 (H-3α),
4.02 (H-4α), 4.01 (H-5α,β), 3.45 (H-6α,β), 4.21 (H-1″β), 3.14
(H-6α), 3.61 (H-6β), 3.67 (H-2α); 13C NMR δppm: 77.0 (C2α),
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79.0 (C2β), 62.1 (C6β). 3,6-di-O-ester: H NMR δppm: 3.61
(H-3α), 3.66 (H-3β), 3.50 (H-6α); 13C NMR δppm: 82.3
(C3α), 83.4 (C3β), 64.8 (C6α).
(H-2″), 3.58 (H-3″), 3.74 (H-4″), 3.46 (H-6″); 13C NMR δppm
:
51.7 (αCH), 37.9 (βCH2), aromatic- 137.8 (C1), 95.6 (C1α),
101.9 (C1β), 71.3 (C2α), 73.2 (C2β), 73.3 (C3α), 74.7 (C3β),
82.2 (C4α), 84.2 (C4β), 77.7 (C5α,β), 62.4 (C6α,β), 103.4
(C1″β), 69.9 (C2″), 72.4 (C3″), 67.4 (C4″), 74.7 (C5″), 62.7
(C6″).
4.4.1.15. L-Phenylalanyl-D-galactose. UV (H2O, λmax):
222.0 nm (σ→σ* ε222.0–871 M–1), 257.5 nm (π→π* ε257.5
437 M–1) and 299.0 nm (n→π* ε299.0 – 331 M–1). IR (KBr):
3379 cm–1 (OH), 1761 cm–1 (C=O), 1603 cm–1 (aromatic, –
C=C–). Optical rotation (c 0.5, H2O): [α]D at 25 °C = +31.1°.
MS (m/z) diester – 512[M + K]+; 13C NMR DMSO-d6 δppm
(125 MHz,): 2-O-ester: 55.7 (αCH), 36.7 (βCH2), aromatic-
136.5 (C1), 127.4 (C2, C6), 129.6 (C3, C5), 129.1 (C4),
171.4 (CO), 97.2 (C1α) 76.3 (C2α), 75.1 (C2β), 60.8 (C6α).
3-O-ester: 13C NMR δppm: 97.2 (C1α), 82.4 (C3α), 81.5
(C3β), 61.0 (C6α). 6-O-ester: 13C NMR δppm: 97.2 (C1α),
70.6 (C2α), 72.2 (C3α), 73.1 (C4α), 63.0 (C6α,β). 2,6-di-O-
ester: 13C NMR δppm: 77.2 (C2αβ), 63.1 (C6β). 3,6-di-O-
ester: 13C NMR δppm: 81.8 (C3α), 62.7 (C6α,β).
4.4.1.18. L-Phenylalanyl-D-mannitol. Solid; UV (H2O, λmax):
215.0 nm (σ→σ* ε215.0–631 M–1), 257.5 nm (π→π* ε257.5
170 M–1). IR (KBr): 3290 cm–1 (OH), 1637 cm–1 (CO),
1532 cm–1 (aromatic, –C=C–). Optical rotation (c 0.6, H2O):
[α]D at 25 °C = +1.6°. MS (m/z) 352 [M + Na]+. 2D-HSQCT
(DMSO-d6): 1-O-ester: 1H NMR δppm (500.13 MHz): 3.48
(αCH), 2.88 (βCH2a), aromatic- 7.26 (H-2, H-6), 7.26 (H-3,
H-5), 7.18 (H-4), 3.38 (H-1), 3.46 (H-2), 3.70 (H-3), 3.84 (H-
4), 3.52 (H-5), 3.36 (H-6); 13C NMR δppm (125 MHz): 55.8
(αCH), 37.1 (βCH2), aromatic- 137.6 (C1), 131.2 (C2, C6),
126.7 (C4), 171.0 (CO), 66.0 (C1, C6), 75.0 (C2), 70.0 (C3),
70.2 (C4), 77.8 (C5). 1,6-di-O-ester: 1H NMR δppm: 3.39
(αCH), 3.46 (H-1), 3.45 (H-2, H-6), 3.11 (H-3, H-4), 3.46
(H-6); 13C NMR δppm: 55.3 (αCH), 66.8 (C1), 77.0 (C2, C5),
70.4 (C3, C4), 66.8 (C6).
4.4.1.16. L-Phenylalanyl-D-fructose. Solid; UV (H2O, λmax):
198.0 nm (σ→σ* ε198.0–4467 M–1) and 257.5 nm (π→π*
ε257.5 776 M–1). IR: 3380 cm–1 (OH), 1630 cm–1 (CO),
1598 cm–1 (aromatic, –C=C–). Optical rotation (c 0.4, H2O):
[α]D at 25 °C = –14.3°. MS (m/z). 365 [M – 1 + K]+. 13C NMR
DMSO-d6 δppm (125 MHz): 1-O-ester: 55.1 (αCH), aromatic-
138.4 (C1), 64.9 (C1α,β), 102.4 (C2β), 76.2 (C4β), 69.6 (C5β),
62.3 (C6α,β). 6-O-ester: 13C NMR δppm: 55.0 (αCH), 63.4
(C1α,β), 98.1 (C2β), 75.8 (C4β), 81.4 (C5β), 64.2 (C6α,β).
4.4.1.19. L-Tryptophanyl-D-glucose. Solid; UV (H2O, λmax):
213.0 nm (σ→σ* ε213.0–1479 M–1), 276 nm (π→π* ε276
389 M–1), 315 nm (n→π* ε315 – 118 M–1). IR (KBr):
3523 cm–1 (NH), 3336 cm–1 (OH), 1633 cm–1 (C=O),
1524 cm–1 (aromatic –C=C–). Optical rotation (c 0.6, H2O):
[α]D at 25 °C = –21.7°. MS (m/z) 366.1 [M]+. 2D-HSQCT
(DMSO-d6): 2-O-ester: 1H NMR δppm (500.13 MHz): 2.92
(αCH), 3.06 (βCH2a), Aromatic - 6.96–7.59, 4.6 (H-1α), 3.69
(H-2α), 3.72 (H-2β), 3.68 (H-3α), 3.54 (H-6α,β); 13C NMR
δppm (125 MHz): 53.2 (αCH), 35.0 (βCH2), aromatic-109.4
(C1), 124.2 (C2), 136.0 (C4), 114.6 (C6), 120.8 (C7), 121.1
(C8), 100.8 (C1α), 75.9 (C2α), 76.2 (C2β) 72.9 (C3α), 62.8
(C6α,β). 3-O-ester: 1H NMR δppm: 2.87 (αCH), 2.84 (βCH2),
3.82 (H-2α), 3.92 (H-3α), 3.59 (H-3β), 3.58 (H-6α,β); 13C
NMR δppm: 52.3 (αCH), 35.9 (βCH2), aromatic-109.3 (C1),
124.3 (C2C3), 136.3 (C4), 121.0 (C5), 113.0 (C6), 116.5 (C7),
120.0 (C8), 100.1 (C1α), 101.8 (C1β), 74.2 (C2α), 71.2 (C2β),
4.4.1.17. L-Phenylalanyl-lactose. Solid; UV (H2O, λmax):
214.0 nm (σ→σ* ε214.0–6026 M–1), 257.5 nm (π→π* ε257.5
562 M–1) and 290.0 nm (n→π* ε290.0 – 302 M–1). IR (KBr):
3378 cm–1 (OH), 1632 cm–1 (CO), 1556 cm–1 (aromatic, –
C=C–). Optical rotation (c 0.2, H2O): [α]D at 25 °C = +31.3°.
MS (m/z) 512 [M + Na]+. 2D-HSQCT (DMSO-d6): 6-O-ester:
1H NMR δppm (500.13 MHz): 2.67 (αCH), 2.89 (βCH2a), aro-
matic- 7.25 (H-2,H-6), 7.28 (H-3,H-5), 7.20 (H-4), 4.32 (H-
1α), 4.23 (H-1β), 3.36 (H-2α), 3.49 (H-2β), 3.32 (H-3α), 3.80
(H-3β), 3.56 (H-4α), 3.72 (H-4β), 3.90 (H-5α,β), 3.47 (H-
6α,β), 4.16 (H-1″β), 3.14 (H-2″), 3.42 (H-3″), 3.62 (H-4″),
3.39 (H-5″), 3.54 (H-6″); 13C NMR δppm (125 MHz): 51.9
(αCH), 38.2 (βCH2) aromatic- 138.0 (C1), 128.3 (C2, C6),
129.1 (C3, C5), 126.1 (C4), 172.5 (CO), 96.6 (C1α), 101.2
(C1β), 70.5 (C2α), 73.0 (C2β), 74.0 (C3β), 82.5 (C4α), 83.3
(C4β), 77.2 (C5α,β), 62.1 (C6αβ), 103.2 (C1″β), 69.9 (C2″),
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82.0 (C3α,β), 62.5 (C6α,β). 6-O-ester: H NMR δppm: 2.81
(αCH), 2.70 (βCH2), 3.41 (H-2α), 3.51 (H-2β), 3.68 (H-3α),
3.52 (H-4α), 3.64 (H-5α), 3.70 (H-5β), 3.65 (H-6α,β); 13C
NMR δppm: 51.5 (αCH), 31.0 (βCH2), aromatic- 109.2
(C1),124.4 (C2,C3), 136.4 (C4), 121.0 (C5), 111.5 (C6), 118.2
(C7), 118.5 (C8), 172.0 (CO), 96.9 (C1α), 101.9 (C1β), 71.8
(C2α), 69.5 (C2β), 72.6 (C3α), 69.6 (C4α), 68.9 (C5α), 70.2
(C5β), 63.0 (C6α,β). 2,6-di-O-ester: 1H NMR δppm: 2.78
(βCH2), 3.92 (H-2α), 3.82 (H-2β), 3.54 (H-6α,β). 13C NMR
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71.6 (C3″), 68.2 (C4″), 74.4 (C5″), 60.5 (C6″). 6″-O-ester: H
NMR δppm: 2.72 (αCH), 3.00 (βCH2a), 5.16 (H-1α), 4.32 (H-
1β), 3.16 (H-2α), 3.45 (H-2β), 3.43 (H-3α), 3.50 (H-3β), 3.32
(H-4α), 3.80 (H-5α,β), 3.49 (H-6α,β), 4.15 (H-1″β), 3.36 (H-
2″), 3.89 (H-4″), 3.89 (H-5″), 3.45 (H-6″); 13C NMR δppm
:
52.5 (αCH), 37.1 (βCH2) Aromatic- 137.6 (C1), 92.0 (C1α),
97.1 (C1β), 69.7 (C2α), 72.7 (C2β), 72.1 (C3α), 74.5 (C3β),
79.9 (C4α), 80.7 (C4β), 76.0 (C5α,β), 61.0 (C6α,β), 104.0
(C1″β), 69.3 (C2″), 72.1 (C3″), 66.3 (C4″), 75.0 (C5″), 63.1
δppm: 31.0 (βCH2), 77.0 (C2α), 77.3 (C2β), 63.2 (C6α,β). 3,6-
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di-O-ester: H NMR δppm 2.82 (αCH), 2.61 (βCH2), 3.74 (H-
3α), 3.44 (H-6α,β); 13C NMR δppm: 51.8 (αCH), 31.0 (βCH2),
81.2 (C3α), 63.9 (C6α,β).