as a pale yellow powder (856 mg, 73%), mp 134–136 °C; νmax
/
(930 mg, 74%), mp 112–114 °C; νmax/cm−1 (KBr) 3474, 2991,
2951, 1749, 1713, 1631, 1597, 1511, 1265, 1138, 1170, 1075;
δH (CDCl3): 1.28 (3H,s, CH3), 1.29 (3H, s, CH3), 2.05 (1H, t,
J 13.2, 6-HH), 2.55 (1H, dd, J 13.2, 2-HH), 2.78 (1H, dd,
J 13.7, 2.3, 6-HH), 3.78 (1H, t, J 10.1, 4-H), 3.99 (1H, ddd,
J 12.8, 9.6, 5.8, 3-H), 4.62 (4H, m, CAr–OCH2), 4.65 (4H, m,
CAr–OCH2), 5.29 (4H, m, CHHvCH), 5.43 (4H, m,
CHHvCH), 6.07 (4H, m, CH2vCH), 6.22 (1H, d, J, 16.1, CAr–
CHvCH), 6.30 (1H, d, J 15.6, CAr–CHvCH), 6.85 (1H, d,
J 8.7, CArH), 6.87 (1H, d, J 7, CArH), 7.06 (4H, m, CArH), 7.57
(1H, J 16.1, CAr–CH), 7.62 (1H, J 15.6, CAr–CH); δC (CDCl3):
17.7 (CH3), 17.7 (CH3), 34.7 (C-2), 36.4 (C-6), 47.8 (COCH3),
48.1 (COCH3), 52.8 (COOCH3), 65.2 (C-3), 68.4 (C-5), 69.7
(CAr-OCH2), 69.7 (CAr–OCH2), 69.9 (CAr–OCH2), 70.1 (CAr–
OCH2), 73.3 (C-4), 78.9 (C-1), 99.8 (COCH3), 99.8 (COCH3),
112.4 (CAr), 113.3 (CAr), 113.5 (CAr), 114.5 (CAr), 115.6 (CH–
COO), 117.9 (CH–COO), 118.0 (CH2vCH), 118.1 (CH2vCH),
118.1 (CH2vCH), 122.9 (CAr), 123.5 (CAr), 127.3 (CAr–CH),
127.5 (CAr–CH), 132.9 (CH2vCH), 133.1 (CH2vCH), 133.2
(CH2vCH), 145.1 (CAr–CH), 146.6 (CAr–CH), 148.6 (CAr–
OCH2), 148.7 (CAr–OCH2), 150.8 (CAr–OCH2), 151.0 (CAr–
OCH2), 165.5 (CH–COO), 166.1 (CH–COO), 170.9 (COOCH3);
HRMS (ESI+): Exact mass calculated for C44H52O14Na
[M + Na+]+, 827.3255. Found 827.3256.
cm−1 (KBr) 3544v, 2993, 2952, 2833, 1749, 1714, 1631, 1597,
1511, 1264, 1139, 1035; δH (CDCl3): 3.92 (3H, s, CAr–OCH3),
4.66 (2H, d, J 5.4, CAr–OCH2), 5.32 (1H, dd, J 10, CHHvCH),
5.41 (1H, d, J 15.6, CHHvCH), 6.07 (1H, m, CH2vCH), 6.45
(1H, d, J 16, CAr–CHvCH), 6.88 (1H, d, J 8.2, CArH), 7.06
(1H, d, J 1.8, CArH), 7.13 (1H, dd, J 8.4, 2.0, CArH), 7.76 (1H,
d, J 16, CAr–CH); δC (CDCl3): 56.1 (CAr–OCH3), 69.8 (CAr–
OCH2), 110.7 (CAr), 112.9 (CAr), 118.7 (CH–COCl), 119.9
(CH2vCH), 124.4 (CAr), 126.3 (CAr–CH), 132.5 (CH2vCH),
149.9 (CAr–CH), 151.8 (CAr–OCH3), 151.8 (CAr–OCH2) 166.1
(COCl).
Synthesis of methyl 3-O-(3,4-di-O-allyl)-caffeoyl-TMB-muco-
quinate 12. To a solution of methyl TMB-muco-quinate 10 (1 g,
3.12 mmol) and DMAP (77 mg, 0.63 mmol) in DCM (50 mL)
were added pyridine (10 mL) and acid chloride 7 (1.30 g,
4.68 mmol) at room temperature. The reaction mixture was
refluxed for 36 h and acidified with a 1 M HCl solution to pH =
3. The layers were separated and the aqueous phase was
extracted with DCM (3 × 50 mL). The combined organic layers
were dried over Na2SO4, filtered and the solvent was removed
in vacuo. The crude product was purified by column chromato-
graphy on silica gel (ethyl acetate–petroleum ether, 20–40%) to
give methyl 3-O-(3,4-di-O-allyl)-caffeoyl-TMB-muco-quinate
12 as a pale yellow powder (1.66 g, 95%), mp 82–84 °C; νmax
/
Synthesis of methyl 1-O-(4-O-allyl)-feruloyl-3-O-(3,4-di-O-
allyl)-caffeoyl-TMB-muco-quinate 16. To a solution of methyl
3-O-(3,4-di-O-allyl)-caffeoyl-TMB-muco-quinate 12 (600 mg,
1.07 mmol) and DMAP (100 mg, 0.82 mmol) in DCM (50 mL)
were added triethylamine (15 mL) and acid chloride 8 (541 mg,
2.14 mmol) at room temperature. The reaction mixture was
refluxed for 36 h and acidified with a 1 M HCl solution to pH =
3. The layers were separated and the aqueous phase was
extracted with DCM (3 × 50 mL). The combined organic layers
were dried over Na2SO4, filtered and the solvent was removed
in vacuo. The crude product was purified by column chromato-
graphy on silica gel (ethyl acetate–petroleum ether, 20–40%) to
give methyl 1-O-(4-O-allyl)-feruloyl-3-O-(3,4-di-O-allyl)-caf-
feoyl-TMB-muco-quinate 16 as a pale yellow powder (605 mg,
73%), mp 101–102 °C; νmax/cm−1 (KBr) 3423, 1992, 2951,
3080, 1749, 1713, 1631, 1597, 1264, 1139; δH (CDCl3): 1.27
(3H, s, CH3), 1.28 (3H, s, CH3), 1.90 (1H, dd, J 13.6, 11.5,
6-HH), 2.04 (1H, t, 12.8, 2-HH), 2.55 (1H, ddd, J 12.4, 6.9,
2-HH), 2.78 (1H, ddd, J 11.4, 6.8, 6-HH), 3.21 (3H, s, CH3,
COCH3), 3.28 (3H, s, CH3, COCH3), 3.72 (3H,s, CH3,
COOCH3), 3.8 (1H, t, J 10.1, 4-H), 3.9 (3H, s, CH3, CAr–
OCH3), 3.97 (1H, ddd, J 14.1, 10, 4.5, 3-H), 4.64 (6H, m, CAr–
OCH2), 5.3 (3H, m, CHHvCH), 5.4 (1H, dd, J 8, 1.37,
CHHvCH), 5.41 (1H, dd, J 11, 1.37, CHHvCH), 5.45 (1H,
dd, J, 11.9, 1.8, CHHvCH), 6.06 (4H, m CH2vCH), 6.25 (1H,
d, J 16.0, CAr–CHvCH), 6.30 (1H, d, J 15.6, CAr–CHvCH),
6.83 (1H, d, J 8.7, CArH), 6.86 (1H, d, J 8.2, CArH), 7.02 (2H, s,
CArH), 7.05 (1H, dd, J 5.1, 2.3, CArH), 7.08 (1H, dd, J 7.8, 1.8,
CArH), 7.59 (1H, d, J 16.0, CAr–CH), 7.62 (1H, d, J 16.0, CAr–
CH); δC (CDCl3): 17.7 (CH3), 17.7 (CH3), 34.7 (C-2), 36.4
(C-6), 47.8 (COCH3), 48.0 (COCH3), 52.8 (COOCH3), 56.0
(CAr–OCH3), 65.2 (C-3), 68.4 (C-5), 69.8 (CAr–OCH2), 69.8
(CAr–OCH2), 70.0 (CAr–OCH2), 73.2 (C-4), 78.8 (C-1), 99.7
(COCH3), 99.8 (COCH3), 110.1 (CAr), 112.4 (CAr), 112.9 (CAr),
cm−1 (KBr) 3423, 2951, 2992, 3080, 1749, 1713, 1631, 1597,
1511, 1264, 1139, 1076; δH (CDCl3): 1.28 (6H, s, CH3), 1.85
(2H, m, 6-HH, 2-HH), 1.99 (1H, t, J 12.4, 6-HH), 2.23 (1H, m,
2-HH), 3.16 (1H, m, 2-HH), 3.24 (6H, s, COCH3), 3.31 (3H, s,
COOCH3), 3.77 (1H, t, J 10, 4-H), 4.10 (1H, ddd, J 14.2, 12.3,
5, 3-H), 4.6 (4H, m, CAr–OCH2), 5.29 (2H, d, J 9.62,
CHHvCH), 5.43 (2H, d, J 16.9, CHHvCH), 6.06 (2H, m,
CH2vCH), 6.21 (1H, d, J 16, CAr–CHvCH), 6.85 (1H, d,
J 8.7, CArH), 7.04 (2H, m, CArH), 7.56 (1H, d, J 16, CAr–CH);
δC (CDCl3): 17.7 (CH3), 17.8 (CH3), 37.5 (C-2), 38.7 (C-6),
47.7 (COCH3), 47.9 (COCH3), 53.2 (COOCH3), 65.5 (C-3),
69.2 (C-5), 69.7 (CAr–OCH2), 70.0(CAr–OCH2), 73.2 (C-4),
73.46 (C-1), 99.6 (COCH3), 99.9 (COCH3), 112.9 (CAr), 113.5
(CAr), 115.9 (CH–COO), 117.9 (CH2vCH), 117.9 (CH2vCH),
122.4 (CAr), 127.6 (CAr–CH), 132.9 (CH2vCH), 133.2
(CH2vCH), 144.8 (CAr–CH), 148.6 (CAr–OCH2), 150.7 (CAr–
OCH2), 166.2 (CH–COO), 175.3 (COOCH3); HRMS (ESI+):
Exact mass calculated for C29H38O11Na [M + Na+]+, 585.2155.
Found 559.2154.
Synthesis of methyl 1,3-di-O-(3,4-di-O-allyl)-caffeoyl-methyl-
TMB-muco-quinate 14. To a solution of methyl TMB-muco-
quinate 10 (500 mg, 1.56 mmol) and DMAP (77 mg,
0.63 mmol) in DCM (50 mL) were added triethylamine (15 mL)
and acid chloride 7 (1.48 g, 5.30 mmol) at room temperature.
The reaction mixture was refluxed for 36 h and acidified with a
1 M HCl solution to pH = 3. The layers were separated and the
aqueous phase was extracted with DCM (3 × 60 mL). The com-
bined organic layers were dried over Na2SO4, filtered and the
solvent was removed in vacuo. The crude product was purified
by column chromatography on silica gel (ethyl acetate–pet-
roleum ether, 20–40%) to give methyl 1,3-di-O-(3,4-di-O-allyl)-
caffeoyl-TMB-muco-quinate 14 as
a pale yellow powder
5274 | Org. Biomol. Chem., 2012, 10, 5266–5277
This journal is © The Royal Society of Chemistry 2012