Molecules 2018, 23, 41
9 of 18
74.2, 74.1, 72.6, 72.2, 72.0, 71.8, 70.8, 68.2, 67.3, 66.5, 64.6, 37.8, 34.0, 31.8, 31.3, 29.7, 29.3 (two), 29.2,
28.3, 27.6, 26.3, 26.1, 24.5, 22.6, 22.3, 21.0 (two), 20.9, 17.4, 17.2, 16.5, 14.1, 13.9; HRESIMS calcd for
C49H78O20Na [M + Na]+ 1009.4984; found, 1009.4988.
1-Octyloxy-4-O-hexanoyl-2-O-levulinoyl-
α
-L-rhamnopyranosyl-(1
-L-rhamnopyranoside (28). 88% for two steps; 1H-NMR (CDCl3):
5.16 (dd, 1H, J = 10.2, 3.4 Hz, H-3000), 5.12 (dd, 1H, J = 3.3, 1.7 Hz, H-2000), 5.08 (dd, 1H, J = 3.4, 1.8
→
3)-2,4-di-O-acetyl-α-L-rhamnopyranosyl-
(1
→
3)-2,3-di-O-acetyl-4-O-levulinoyl-α
δ
Hz, H-200), 5.04 (t, 1H, J = 9.9 Hz, H-4000), 5.03 (t, 1H, J = 9.9 Hz, H-400), 5.02 (t, 1H, J = 9.9 Hz, H-40),
4.99 (dd, 1H, J = 3.2, 1.6 Hz, H-20), 4.97 (d, 1H, J = 1.7 Hz, H-1000), 4.84 (d, 1H, J = 1.3 Hz, H-100), 4.64
(d, 1H, J = 1.5 Hz, H-10), 4.10 (dd, 1H, J = 10.2 3.4 Hz, H-300), 4.05 (dd, 1H, J = 10.0, 3.4 Hz, H-30),
3.74–3.84 (m, 3H, H-50, H-500, H-5000), 3.61–3.65 (m, 1H, H-1-1), 3.36–3.40 (m, 1H, H-1-2), 2.68–2.78 (m,
6H, 3
COCH2-2), 2.21, 2.18, 2.16, 2.15, 2.11, 2.01 (each s, each 3H, each CH3CO), 1.55–1.64 (m, 4H, 2
1.26–1.33 (m, 14H, 7
J = 6.2 Hz, H-60), 0.89 (t, 3H, J = 7.0 Hz, CH3), 0.89 (t, 3H, J = 7.2 Hz, CH3); 13C-NMR (CDCl3):
×
COCH2), 2.53 (td, 2H, J = 6.4, 2.2 Hz, COCH2), 2.42–2.47 (m, 1H, COCH2-1), 2.31–2.36 (m, 1H,
×
CH2),
×
CH2), 1.18 (d, 3H, J = 6.2 Hz, H-6000), 1.17 (d, 3H, J = 6.2 Hz, H-600), 1.14 (d, 3H,
δ
206.1,
206.0, 173.0, 171.9, 171.8, 170.4, 170.2, 170.0, 169.9, 99.4, 98.6, 97.2, 75.2, 74.7, 72.2, 71.9, 71.8, 71.4, 71.0,
70.1, 68.4, 68.2 (two), 67.3, 67.1, 66.6, 37.6, 34.0, 31.8, 31.3, 29.7 (two), 29.3 (two), 28.2, 27.9, 26.1, 24.5,
22.6, 22.3, 20.9 (two), 20.8, 20.7, 17.5, 17.2, 17.1, 14.1, 13.9; HRESIMS calcd for C50H78O22Na [M + Na]+
1053.4882; found, 1053.4893.
1-Octyloxy-2,3,4-tri-O-acetyl-
α
-L-rhamnopyranosyl- (1
→
3)-2,4-di-O-acetyl-
α
-L-rhamnopyranosyl-(1
→
3)-4-O-
hexanoyl-2-O-levulinoyl-
α
-L-rhamnopyranoside (29). 89% for two steps; 1H-NMR (CDCl3):
δ 5.15 (dd,
1H, J = 10.2, 3.4 Hz, H-3000), 5.13 (dd, 1H, J = 3.2, 1.6 Hz, H-2000), 5.10 (dd, 1H, J = 3.2, 1.8 Hz, H-200),
5.07 (t, 1H, J = 9.8 Hz, H-4000), 5.01–5.06 (m, 2H,0H-40, H-400), 4.98–4.99 (m 2H, H-20, H-1000), 4.84 (d,
1H, J = 1.7 Hz, H-100), 4.65 (d, 1H, J = 1.4 Hz, H-1 ), 4.11 (dd, 1H, J = 10.0, 3.4 Hz, H-300), 4.06 (dd, 1H,
J = 10.0, 3.1 Hz, H-30), 3.75–3.78 (m, 3H, H-50, H-500, H-5000), 3.61–3.65 (m, 1H, H-1-1), 3.37–3.41 (m, 1H,
H-1-2), 2.77 (t, 2H, J = 6.1 Hz, COCH2), 2.66–2.72 (m, 2H, CH2CO), 2.30–2.78 (m, 2H, CH2CO), 2.22,
2.17, 2.15, 2.13, 2.05, 1.97 (each s, each 3H, each CH3CO), 1.55–1.66 (m, 4H, 2
×
CH2), 1.28–1.33 (m,
CH2), 1.18 (d, 3H, J = 6.2 Hz, H-6 ), 1.17 (d, 6H, J = 6.2 Hz, H-6 , H-6 ), 0.90 (t, 6H, J = 7.0 Hz
CH3); 13C-NMR (CDCl3):
206.0, 173.0, 171.9, 170.4, 170.2, 170.1, 170.0, 169.7, 99.4, 98.7, 97.2, 75.2,
0
00
000
14H, 7
×
,
2
×
δ
74.8, 72.3, 71.9, 71.8, 71.4, 70.9, 70.0, 68.7, 68.2, 67.3, 67.1, 66.5, 37.7, 34.0, 31.8, 31.3, 29.7 (two), 29.3
(two), 29.2, 28.2, 26.1, 24.5, 22.6, 22.3, 20.9 (two), 20.8, 20.7, 17.5, 17.2 (two), 14.1, 13.9; HRESIMS calcd
for C47H74O21Na [M + Na]+ 997.4620; found, 997.4630.
1-Octyloxy-2-O-acetyl-3,4-di-O-levulinoyl-
α
-L-rhamnopyranosyl-(1
→
3)-2,4-di-O-acetyl-
α
-L-rhamnopyranosyl-
1
(1→
3)-4-O-hexanoyl-2-O-levulinoyl-
α
-L-rhamno-pyranoside (30). 84% for two steps; H-NMR (CDCl3):
δ
5.16 (dd, 1H, J = 10.3, 3.4 Hz, H-3000), 5.12 (dd, 1H, J = 3.3, 1.7 Hz, H-2000), 5.06 (t, 1H, J = 9.8 Hz,
H-4000), 5.05 (dd, 1H, J = 3.4, 1.7 Hz, H-200), 5.04 (t, 1H, J = 9.9 Hz, H-400), 5.03 (t, 1H, J = 9.9 Hz, H-40),
4.98 (dd, 1H, J = 3.4, 1.6 Hz, H-20), 4.47 (d, 1H, J = 1.7 Hz, H-1000), 4.83 (d, 1H, J = 1.4 Hz, H-100), 4.65
(d, 1H, J = 1.6 Hz, H-10), 4.10 (dd, 1H, J = 10.1, 3.4 Hz, H-300), 4.05 (dd, 1H, J = 10.1, 3.4 Hz, H-30),
3.73–3.83 (m, 3H, H-50, H-500, H-5000), 3.61–3.65 (m, 1H, H-1-1), 3.37–3.40 (m, 1H, H-1-2), 2.31–2.78 (m,
14H, 7 × COCH2), 2.21, 2.18, 2.16, 2.16, 2.14, 2.12 (each s, each 3H, each COCH3), 1.55–1.65 (m, 4H,
2 × CH2), 1.25–1.33 (m, 14H, 7
×
CH2), 1.18 (d, 3H, J = 6.2 Hz, H-60), 1.17 (d, 3H, J = 6.2 Hz, H-600),
1.16 (d, 3H, J = 6.2 Hz, H-6000), 0.90 (t, 3H, J = 7.0 Hz, CH3), 0.89 (t, 3H, J = 7.0 Hz, CH3); 13C-NMR
(CDCl3): 206.4 (two), 173.0, 172.0, 171.9, 171.4, 170.4, 170.2, 170.0, 99.4, 98.7, 97.2, 75.2, 74.8, 72.2, 71.9,
δ
71.8, 71.4, 70.8, 70.0, 68.7, 68.1, 67.3, 67.1, 66.5, 37.8, 37.7 (two), 34.0, 31.8, 31.3, 29.7, 29.3 (two), 29.2,
28.2, 27.9, 27.8, 26.1, 24.5, 22.6, 22.3, 20.9 (two), 20.8, 17.5, 17.2, 17.1, 14.1, 13.9; HRESIMS calcd for
C53H82O23Na [M + Na]+ 1109.5145; found, 1109.5156.
3.2.4. General Method A for Removal of the Lev Protecting Groups
To a stirred solution of Lev protected compound (1.0 mmol) in 20 mL dry CH2Cl2-MeOH (v:v = 1:1)
hydrazine acetate (10 mmol)was added. After stirring at room temperature for 5 h, the reaction mixture