K.-i. Oyama et al. / Tetrahedron xxx (2014) 1e11
7
3.72 (dd, J¼10.0, 3.0 Hz, 1H), 3.79 (s, 3H), 4.43 (ddd, J¼12.0, 10.0,
4.9. Compound 14a and 4-methoxybenzyl (20S,30S)-3-O,4-O-
(20,30-dimethoxybutane-20,30-diyl)-1-O-naphthoylquinate
(14b)
4.0 Hz, 1H), 5.09 (d, J¼12.0 Hz, 1H), 5.14 (d, J¼12.0 Hz, 1H), 5.44 (q,
J¼3.0 Hz, 1H), 6.32 (d, J¼16.5 Hz, 1H), 6.36 (d, J¼16.5 Hz, 1H), 6.85
(d, J¼8.5 Hz, 2H), 7.12 (t, J¼7.5 Hz, 2H), 7.20e7.26 (m, 5H), 7.25 (d,
J¼8.5 Hz, 2H), 7.31e7.36 (m, 3H), 7.63 (d, J¼16.0 Hz, 1H), 7.64 (d,
According to the procedure described for 10a (method B, Table
3, entry 3), 11 (65 mg, 0.376 mmol) was esterified with 4
(107 mg, 0.25 mmol) to afford 14a (122 mg, 84%) and 14b (13 mg,
7%), respectively (solvent used for flash column chromatography:
20e30% AcOEt in hexane).
J¼16.0 Hz, 1H); 13C NMR (150 MHz, CDCl3)
d 17.6, 17.8, 32.6, 36.7,
47.9, 48.0, 55.2, 62.8, 67.4, 68.8, 70.9, 79.7, 99.8, 100.1, 114.0, 117.6,
118.3, 127.4, 127.9, 128.1, 128.7, 128.9, 130.0, 130.2, 130.4, 133.9,
134.2, 145.0, 145.8, 159.7, 165.1, 166.2, 170.5; HRMS (FAB) calcd for
C
39H42O11Na [MþNa]þ 709.2625, found 709.2623.
4.9.1. Compound 14b. White solid; mp: 152e154 ꢁC; [
a
]
22 þ97.0 (c
D
0.2, CHCl3); IR (KBr) 2961, 2834, 1715, 1614, 1516, 1466, 1305, 1198,
4.7. Compounds 10a and 10b (method B, Table 3, entry 3)
1112, 930, 825 cmꢀ1; UV (CHCl3) lmax/nm (
3
), 247 (26,000); 1H NMR
(500 MHz, CDCl3)
d
1.25 (s, 3H), 1.34 (s, 3H), 2.13 (dd, J¼13.5, 12.0
To a solution of cinnamic acid 9 (74 mg, 0.5 mmol), TsCl
(191 mg, 1.0 mmol), and MS 4 A (ca. 0.8 g) in dichloroethane
(1.5 mL) was added i-Pr2NEt (262 mL, 1.5 mmol) at room temper-
ature and the resulting mixture was stirred for 30 min at this
temperature. To the reaction mixture was added a solution of al-
cohol 4 (107 mg, 0.25 mmol) in dichloroethane (1.8 mL) and
Hz, 1H), 2.37 (dd, J¼16.5, 3.5 Hz, 1H), 2.71 (td, J¼13.5, 3.5 Hz, 1H),
3.21 (td, J¼16.5, 3.5 Hz, 1H), 3.28 (s, 3H), 3.40 (s, 3H), 3.76 (s, 3H),
3.82 (dd, J¼10.5, 3.5 Hz,1H), 4.72 (ddd, J¼12.0, 10.5, 3.5 Hz,1H), 5.11
(d, J¼12.0 Hz,1H), 5.16 (d, J¼12.0 Hz,1H), 5.56 (q, J¼3.5 Hz,1H), 6.80
(d, J¼8.5 Hz, 2H), 7.11e7.15 (m, 2H), 7.22 (d, J¼8.5 Hz, 1H), 7.26e7.29
(m, 3H), 7.27 (d, J¼8.5 Hz, 2H), 7.34 (d, J¼8.5 Hz, 1H), 7.37 (ddd,
J¼8.0, 6.3, 1.5 Hz, 1H), 7.26e7.29 (m, 3H), 7.42 (td, J¼8.0, 1.0 Hz, 1H),
7.47 (t, J¼8.5 Hz, 1H), 7.55 (d, J¼8.0 Hz, 1H), 7.70 (dd, J¼8.5, 1.5 Hz,
1H), 7.75 (dd, J¼8.5, 1.5 Hz, 1H), 8.24 (s, 1H), 8.35 (s, 1H); 13C NMR
ꢀ
subsequently NMI (120
mL, 1.5 mmol) was added at room tem-
perature. After stirring for 2 h at 40 ꢁC, the reaction mixture was
quenched with saturated aqueous NH4Cl. The crude products were
extracted with AcOEt. The combined extracts were washed with
saturated aqueous NaHCO3, and dried over anhydrous Na2SO4. The
solvent was concentrated under reduced pressure and the residue
was purified by flash column chromatography (30% AcOEt in
hexane) to give 10a (122 mg, 87%) and 10b (9 mg, 5%),
respectively.
(125 MHz, CDCl3)
d 17.6, 17.8, 33.3, 36.5, 47.9, 48.1, 55.2, 62.7, 67.4,
70.0, 71.3, 80.3, 99.8, 100.0, 113.9, 124.7, 125.0, 126.1, 126.5, 127.3,
127.4, 127.6, 127.7, 127.8, 128.0, 128.9, 130.1, 131.0, 131.1, 131.9, 132.1,
135.1, 135.2, 159.7, 165.2, 166.4, 170.5; HRMS (FAB) calcd for
C
43H42O11Na [MþNa]þ 757.2625, found 757.2601.
4.10. 4-Methoxybenzyl (20S,30S)-5-O-benzoyl-3-O,4-O-(20,30-di-
methoxybutane-20,30-diyl)quinate (16a) and 4-methoxybenzyl
(20S,30S)-1,5-O-dibenzoyl-3-O,4-O-(20,30-dimethoxybutane-
20,30-diyl)quinate (16b)
4.8. 4-Methoxybenzyl (20S,30S)-3-O,4-O-(20,30-dimethox-
ybutane-20,30-diyl)-5-O-naphthoylquinate (14a) and 1-methyl-
2-naphthoylimidazole (15)
According to the procedure described for 10a (method B, Table
3, entry 3), 12 (60 mg, 0.495 mmol) was esterified with 4
(192 mg, 0.45 mmol) to afford 16a (225 mg, 94%) and 16b (9 mg,
3%), respectively (solvent used for flash column chromatography:
20e30% AcOEt in hexane).
According to the procedure described for 10a (method A, Table
2, entry 3), 11 (241 mg, 1.41 mmol) was esterified with 4 (300 mg,
0.7 mmol) to afford 14a (352 mg, 86%) and 15 (115 mg, 35% based on
11), respectively (solvent used for flash column chromatography:
20e30% AcOEt in hexane).
25
4.10.1. Compound 16a. Colorless amorphous; [
a]
þ31.2 (c 0.5,
D
23
4.8.1. Compound 14a. Colorless amorphous; [
a
]
þ62.1 (c 1.0,
CHCl3); IR (KBr) 3507, 2951, 2834, 1717, 1612, 1516, 1452, 1374, 1282,
1127, 714 cmꢀ1; UV (CHCl3) lmax/nm ( ), 241 (9400); 1H NMR
(400 MHz, CDCl3)
1.22 (s, 3H), 1.28 (s, 3H), 2.02 (d, J¼8.5 Hz, 2H),
D
CHCl3); IR (KBr) 3487, 2952, 2837, 1715, 1515, 1284, 1233,
1131 cmꢀ1; UV (CHCl3) lmax/nm ( ), 246 (27,000); 1H NMR
(600 MHz, CDCl3)
1.23 (s, 3H), 1.30 (s, 3H), 2.06 (d, J¼8.5 Hz,
3
3
d
d
2.14 (dd, J¼15.4, 3.2 Hz, 1H), 2.25 (td, J¼15.4, 1.2 Hz, 1H), 3.20 (br s,
1H, OH), 3.25 (s, 3H), 3.30 (s, 3H), 3.72 (dd, J¼10.2, 3.2 Hz, 1H), 3.82
(s, 3H), 4.54 (td, J¼10.2, 8.5 Hz, 1H), 5.09 (d, J¼12.0 Hz, 1H), 5.15 (d,
J¼12.0 Hz, 1H), 5.46 (q, J¼3.2 Hz, 1H), 6.89 (d, J¼8.5 Hz, 2H), 7.26 (d,
J¼8.5 Hz, 2H), 7.41e7.46 (m, 2H), 7.52e7.57 (m, 1H), 8.08 (dd, J¼8.6,
2H), 2.19 (dd, J¼15.4, 3.0 Hz, 1H), 2.32 (brd, J¼15.4 Hz, 1H), 3.27
(s, 3H), 3.35 (s, 3H), 3.76 (dd, J¼10.0, 3.0 Hz, 1H), 3.82 (s, 3H), 4.63
(td, J¼10.0, 8.5 Hz, 1H), 5.11 (d, J¼12.0 Hz, 1H), 5.16 (d, J¼12.0 Hz,
1H), 5.51 (q, J¼3.0 Hz, 1H), 6.89 (d, J¼7.0 Hz, 2H), 7.27 (d,
J¼7.0 Hz, 2H), 7.53 (t, J¼8.0 Hz, 1H), 7.58 (t, J¼8.0 Hz, 1H), 7.88 (d,
J¼8.0 Hz, 1H), 7.95 (d, J¼8.0 Hz, 1H), 8.10 (d, J¼8.0 Hz, 1H), 8.66 (s,
1.5 Hz, 2H); 13C NMR (150 MHz, CDCl3)
d 17.6, 17.8, 36.7, 38.7, 47.9,
48.0, 55.3, 62.8, 67.9, 70.1, 71.4, 74.5, 99.5, 100.0, 114.1, 127.0, 128.3,
129.9, 130.2, 130.8, 132.8, 160.0, 166.2, 175.1; HRMS (FAB) calcd for
1H); 13C NMR (150 MHz, CDCl3)
d 17.6, 17.8, 36.7, 38.8, 48.0, 55.3,
62.9, 68.0, 70.3, 71.5, 74.5, 99.6, 100.0, 114.1, 125.5, 126.4, 127.0,
127.7, 128.0, 128.1, 129.4, 130.2, 131.5, 132.6, 135.5, 160.0, 166.4,
175.1; HRMS (FAB) calcd for C32H36O10Na [MþNa]þ 603.2206,
found 603.2198.
C
28H34O10Na [MþNa]þ 553.2050, found 553.2039.
25
4.10.2. Compound 16b. Colorless amorphous; [
CHCl3); IR (KBr) 2949, 2835, 1719, 1517, 1282, 1126, 710 cmꢀ1; UV
(CHCl3) lmax/nm ( 1.21 (s,
), 241 (7400); 1H NMR (600 MHz, CDCl3)
a
]
þ56.3 (c 0.5,
D
3
d
4.8.2. Compound 15. Pale yellow oil; IR (neat) 3058, 2957, 1638,
3H), 1.30 (s, 3H), 2.07 (dd, J¼13.0, 12.5 Hz, 1H), 2.31 (dd, J¼16.0,
3.5 Hz, 1H), 2.63 (td, J¼13.0, 3.5 Hz,1H), 3.04 (td, J¼16.0, 3.5 Hz,1H),
3.26 (s, 3H), 3.28 (s, 3H), 3.79 (s, 3H), 3.76 (dd, J¼10.0, 3.5 Hz, 1H),
4.54 (ddd, J¼13.0, 10.0, 3.5 Hz, 1H), 5.09 (d, J¼12.0 Hz, 1H), 5.13 (d,
J¼12.0 Hz, 1H), 5.54 (q, J¼3.5 Hz, 1H), 6.82 (d, J¼8.8 Hz, 2H), 7.11 (t,
J¼8.0 Hz, 2H), 7.18 (t, J¼8.0 Hz, 2H), 7.21 (d, J¼8.8 Hz, 2H), 7.39e7.43
1466, 1401, 1274, 1236, 1162, 1118, 903, 781 cmꢀ1
;
1H NMR
(500 MHz, CDCl3)
d 4.12 (s, 3H), 7.14 (s, 1H), 7.28 (s, 1H), 7.53 (ddd,
J¼8.3, 7.0, 1.0 Hz, 1H), 7.59 (ddd, J¼8.3, 7.0, 1.0 Hz, 1H), 7.88 (d,
J¼8.5 Hz, 1H), 7.92 (d, J¼8.5 Hz, 1H), 8.01 (d, J¼8.5 Hz, 1H), 8.27 (dd,
J¼8.5, 1.5 Hz, 1H), 8.99 (br s, 1H); 13C NMR (125 MHz, CDCl3)
d 36.4,
125.9, 126.4, 126.7, 127.6, 127.8, 128.3, 129.3, 129.9, 132.4, 133.3,
134.5, 135.4, 143.3, 183.9; HRMS (ESI) calcd for C15H13N2O [MþH]þ
237.1022, found 237.1034.
(m, 2H), 7.78 (dd, J¼8.0, 1.0 Hz, 2H), 7.84 (dd, J¼8.0, 1.0 Hz, 2H); 13
C
NMR (150 MHz, CDCl3)
d 17.5, 17.7, 33.6, 36.3, 47.8, 48.0, 55.2, 62.6,
67.4, 69.6, 71.2, 80.3, 99.7, 100.0, 100.6, 113.9, 127.3, 128.0, 128.1,