The Journal of Organic Chemistry
FEATURED ARTICLE
149.2, 148.4, 148.3, 137.4, 137.3, 137.2, 136.6, 136.5, 127.6, 127.5 (2 C),
127.4 (4 C), 127.2, 127.1, 127.0 (2 C), 126.9, 126.8 (3 C), 126.6, 124.1,
123.0, 122.5, 122.4, 115.3, 113.7, 112.0, 111.9, 100.8, 98.5, 83.5, 80.4,
77.1, 76.2, 74.8, 74.3, 74.1, 73.6, 73.4, 73.4, 72.3, 72.1, 72.0, 70.7, 62.7,
60.9, 55.0, 54.8; HRMS (MALDI) calcd for C70H70O17Na [M þ Na]þ
1205.4505, found 1205.4500.
mixture was stirred at room temperature for 3 h under H2 atmosphere.
Filtration through a pad of Celite and evaporation of the filtrate under
vacuum gave a residue, which was purified by column chromatography on
silica gel (CH2Cl2/MeOH, 6:1) to give 7 (13 mg, 81%) as a white solid:
[R]25D = þ80.8 (c 0.3, pyridine); 1H NMR (500 MHz, CD3SOCD3) δ
7.79 (dd, J= 2.0, 7.0 Hz, 1 H), 7.77 (dd, J= 1.5, 6.0 Hz, 1 H), 7.42 (d, J=2.5
Hz, 1 H), 7.41 (t, J = 3.0 Hz, 2 H), 7.38 (d, J = 9.0 Hz, 1 H), 7.33 (d, J = 9.5
Hz, 1 H), 5.52 (s, 1 H), 5.45 (d, J = 5.0 Hz, 1 H), 5.39 (d, J = 9.0 Hz, 1 H),
5.33 (d, J = 3.0 Hz, 1 H), 5.25 (d, J = 7.5 Hz, 2 H), 5.21 (d, J = 7.0 Hz, 1 H),
5.06 (d, J = 8.0 Hz, 1 H), 4.42 (d, J = 10.0 Hz, 1 H), 4.38 (d, J = 11.5 Hz,
1 H), 4.28ꢀ4.24 (m, 1 H), 4.13ꢀ4.07 (m, 2 H), 3.99ꢀ3.97 (m, 2 H), 3.79
(s, 6 H), 3.58 (m, 1 H), 3.45ꢀ3.39 (m, 3 H), 3.18ꢀ3.16 (m, 1 H); 13C
NMR (125 MHz, CD3SOCD3) δ 165.2, 165.1, 150.1, 149.8, 148.5, 148.4,
123.1, 123.0, 122.5, 122.4, 114.4, 114.3, 112.1, 98.3, 96.8, 76.9, 73.5, 72.8,
71.7, 71.2, 70.6, 69.8, 68.2, 65.4, 65.1, 55.5; HRMS (ESI) calcd for
C28H32O16Na [M þ Na]þ 647.1588, found 647.1600.
Alcoholic Acid 33. Similar procedure as that for 30f32 was used to
convert allyl ester 31 into 33 (42 mg, 87%) as a white solid: [R]25D = þ2.8
(c 0.9, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 1.6 Hz, 1 H),
7.33ꢀ7.16 (m, 33 H), 6.94 (d, J = 8.4 Hz, 1 H), 5.57 (d, J = 8.0 Hz, 1 H),
5.14 (d, J = 10.8 Hz, 1 H), 5.02 (d, J = 11.6 Hz, 1 H), 5.96ꢀ4.75 (m, 7 H),
4.62 (d, J = 12.0 Hz, 1 H), 4.58 (d, J = 11.2 Hz, 1 H), 4.48 (d, J = 11.2 Hz,
1 H), 4.36 (m, 2 H), 4.16 (s, 1 H), 3.92ꢀ3.89 (m, 1 H), 3.80ꢀ3.74 (m, 3 H),
3.76 (s, 3 H), 3.68 (s, 6 H), 3.64 (dd, J = 4.8, 11.6 Hz, 1 H), 3.53ꢀ3.50 (m,
2 H), 3.40 (dd, J = 9.6, 18.0 Hz, 1 H); 13C NMR (100 MHz, CDCl3) δ
164.6, 151.8, 149.4, 148.4, 138.5, 138.0, 137.7, 137.3, 137.2, 136.6, 136.5,
127.6, 127.5, 127.4 (2 C), 127.2, 127.1, 127.0, 126.9 (2 C), 126.8 (2 C),
126.4, 126.3, 124.5, 122.6, 114.8, 112.0, 106.2, 101.4, 100.8, 83.4, 80.4,
78.5, 76.9, 76.2, 74.8, 74.2, 74.1, 73.8, 73.7, 73.3, 72.5, 72.2, 72.0, 70.5, 62.8,
61.0, 55.4, 54.8; HRMS (MALDI) calcd for C71H72O18Na [M þ Na]þ
1235.4611, found 1235.4609.
Clemahexapetoside A (8). Similar procedure as that used for
34f7 was applied to convert 35 into Clemahexapetoside A (8) (20 mg,
100%) as a white solid: [R]25D = þ81.1 (c 0.2, pyridine); 1H NMR (500
MHz, CD3SOCD3) δ 7.50 (d, J = 1.5 Hz, 1 H), 7.36 (d, J = 1.0 Hz, 1 H),
7.08 (d, J = 1.0 Hz, 1 H), 6.99 (d, J = 8.0 Hz, 1 H), 6.82 (dd, J = 1.5, 9.0
Hz, 1 H), 5.61 (d, J = 8.0 Hz, 1H), 5.47 (d, J = 4.5 Hz, 1 H), 5.43 (d, J =
5.0 Hz, 1 H), 5.29 (d, J = 4.0 Hz, 1 H), 5.15 (d, J = 6.5 Hz, 1 H), 5.07 (d,
J= 3.5 Hz, 1H), 5.05 (d, J= 7.0 Hz, 1 H), 4.87 (d, J= 7.5 Hz, 1 H), 4.51 (d, J =
10.5 Hz, 1 H), 4.44ꢀ4.39 (m, 1 H), 4.36 (d, J = 10.0 Hz, 1 H), 3.96 (s,
3 H), 3.94ꢀ3.83 (m, 4 H), 3.79 (s, 3 H), 3.59 (s, 3 H), 3.49ꢀ3.46 (m,
1 H), 3.40ꢀ3.37 (m, 3 H), 3.22ꢀ3.19 (m, 1 H); 13C NMR (125 MHz,
CD3SOCD3) δ 165.2, 164.8, 153.2, 152.0, 149.9, 148.4, 138.1, 124.5,
122.6, 122.3, 114.4, 111.9, 107.0, 106,9, 99.2, 99.0, 77.2, 73.9, 73.0, 71.7,
71.4, 71.0, 70.7, 68.6, 65.4, 64.3, 56.6, 55.9, 55.5; HRMS (ESI) calcd for
C29H34O17Na [M þ Na]þ 677.1688, found 677.1707.
Cyclic Dimer 34. To a solution of 32 (13 mg, 0.01 mmol) and Et3N
(0.08 mL) in dry THF (1.00 mL) was added 2,4,6-trichlorobenzoyl
chloride (0.05 mL, 0.3 mmol). The solution was stirred at room
temperature for 3 h, and then a solution of DMAP (86 mg, 0.72 mmol)
in toluene (40 mL) was added. The resulting mixture was stirred for
another 4hatthesametemperatureandwasthendilutedwithethylacetate
(300 mL). The resulting mixture was washed with saturated NaHCO3,
dried over anhydrous Na2SO4, filtered, and concentrated under reduced
pressure. The residue was subjected to column chromatography on silica
gel (petroleum ether/EtOAc, 3:1) to give 34 (10 mg, 78%) as a white
solid: [R]25D = þ44.6 (c 1.1, CHCl3); 1H NMR (400 MHz, CDCl3) δ
7.68ꢀ7.64 (m, 1 H), 7.48 (dd, J = 2.0, 5.2 Hz, 2 H), 7.39ꢀ7.17 (m, 32 H),
5.61 (d, J = 8.0 Hz, 1 H), 5.15 (d, J = 10.8 Hz, 1 H), 5.06ꢀ4.75 (m, 9 H),
4.61ꢀ4.43 (m, 5 H), 4.34 (d, J = 11.2 Hz, 1 H), 4.20 (t, J = 2.4 Hz, 1 H),
4.09 (t, J = 10.4 Hz, 1 H), 4.01 (t, J = 10.8 Hz, 1 H), 3.88 (dd, J = 1.6, 9.6
Hz, 1 H), 3.80(s,3 H), 3.79(s,3 H), 3.83ꢀ3.74 (m, 2 H), 3.58 (dd, J=2.4,
8.0 Hz, 1 H), 3.44ꢀ3.39 (m, 1 H), 3.31 (dd, J = 2.4, 9.6 Hz, 1 H); 13C
NMR (100 MHz, CDCl3) δ 164.8 (2 C), 149.4, 149.2, 148.4, 148.3, 137.6,
137.4, 137.3, 137.2, 136.5, 136.1, 127.6, 127.5, 127.4, 127.2, 127.1, 127.0,
126.9 (2 C), 126.8 (2 C), 126.7, 126.6, 123.3, 122.7, 122.4, 122.2, 114.2,
114.0, 111.7, 100.1, 97.4, 83.7, 80.2, 77.4, 76.8, 76.2, 74.9, 74.2, 73.9, 73.7,
73.6, 72.3, 72.0, 70.4, 70.0, 64.2, 63.6, 55.0, 54.9; HRMS (MALDI) calcd
for C70H68O16Na [M þ Na]þ 1187.4400, found 1187.4391.
Methyl 4-(20,30,40-Tri-O-benzyl-60-O-trityl-β-D-glucopyra-
nosyloxy)benzoate (37). Similar procedure as that used for
14f15 was applied to convert tetraol 36 into 37 (438 mg, 70% for
two steps) as a white solid: [R]25D = ꢀ25.4 (c 0.9, CHCl3); 1H NMR
(400 MHz, CDCl3) δ 7.97 (d, J = 8.8 Hz, 2 H), 7.40ꢀ7.09 (m, 30 H),
6.81 (d, J = 6.8 Hz, 2 H), 5.05 (d, J = 7.6 Hz, 1 H), 4.99 (d, J = 10.8 Hz,
1 H), 4.86ꢀ4.74 (m, 3 H), 4.64 (d, J = 10.0 Hz, 1 H), 4.29 (d, J = 10.8 Hz,
1 H), 3.82 (s, 3 H), 3.78 (t, J = 8.4 Hz, 1 H), 3.71ꢀ3.61 (m, 2 H),
3.53ꢀ3.51 (m, 2 H), 3.21 (dd, J = 5.2, 10.4 Hz, 1 H); 13C NMR (100
MHz, CDCl3) δ 165.7, 159.9, 142.7, 137.3, 137.1, 136.6, 130.6, 127.7,
127.4, 127.3, 127.2, 127.0, 126.8 (2 C), 126.0, 123.4, 115.4, 100.0, 85.6,
83.6, 81.0, 76.7, 75.0, 74.2, 74.1, 74.0, 61.4, 51.0; HRMS (MALDI) calcd
for C54H50O8Na [M þ Na]þ 849.3398, found 849.3409.
4-(20,30,40-Tri-O-benzyl-60-O-trityl-β-D-glucopyranosyloxy)-
benzoic acid (38). Similar procedure as that used for 24f26 was
applied to convert methyl ester 37 into acid 38 (348 mg, 91%) as a white
solid: [R]25D = ꢀ25.6 (c 1.8, CHCl3); 1H NMR (400 MHz, CDCl3) δ
8.05 (d, J = 9.2 Hz, 2 H), 7.39ꢀ7.10 (m, 30 H), 6.82ꢀ6.80 (m, 2 H),
5.08 (d, J = 7.6 Hz, 1 H), 5.00 (d, J = 11.2 Hz, 1 H), 4.87ꢀ4.75 (m, 3 H),
4.65 (d, J = 10.4 Hz, 1 H), 4.30 (d, J = 10.4 Hz, 1 H), 3.80 (t, J = 8.0 Hz,
1 H), 3.71ꢀ3.64 (m, 2 H), 3.55ꢀ3.53 (m, 2 H), 3.21ꢀ3.20 (m, 1H);
13C NMR (100 MHz, CDCl3) δ 170.6, 160.5, 142.7, 137.3, 137.1, 136.5,
131.3, 127.7, 127.4, 127.3, 127.2, 127.0, 126.9, 126.8, 126.0, 122.6, 115.4,
99.9, 85.6, 83.5, 81.0, 76.7, 75.0, 74.2, 74.1, 74.0, 61.3; HRMS (MALDI)
calcd for C53H48O8Na [M þ Na]þ 835.3241, found 835.3251.
Cyclic Dimer 35. Similar procedure as that for 32f34 was adopted
to convert 33 into 35 (20 mg, 88%) as a white solid: [R]25D = ꢀ9.5 (c 1.2,
1
CHCl3); H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 1.6 Hz, 1 H),
7.37ꢀ7.14 (m, 32 H), 6.82 (dd, J = 1.6, 8.4 Hz, 1 H), 6.76 (d, J = 8.4 Hz,
1 H), 5.46(d, J=8.0 Hz, 1H), 5.20(d, J=11.6 Hz, 1 H), 5.14 (d, J=10.8Hz,
1 H), 4.95 (dd, J = 4.4, 11.6 Hz, 3 H), 4.86ꢀ4.72 (m, 5 H), 4.69 (d, J = 11.6
Hz, 1 H), 4.59 (d, J = 11.2 Hz, 1 H), 4.51 (d, J = 12.0 Hz, 1 H), 4.48 (dd, J =
3.6, 12.4 Hz, 1 H), 4.32 (d, J = 12.0 Hz, 1 H), 4.20 (t, J = 2.4 Hz, 1 H),
4.13ꢀ4.10 (m, 1 H), 3.97ꢀ3.87 (m, 2 H), 3.80 (s, 3 H), 3.79 (s, 3 H),
3.77ꢀ3.72 (m, 3 H), 3.64 (dd, J = 2.4, 8.0 Hz, 1 H), 3.43 (s, 3 H), 3.41 (t, J =
8.8Hz, 1H), 3.33(dd, J= 2.4, 9.6 Hz, 1 H); 13C NMR (100 MHz, CDCl3) δ
165.9, 165.4, 154.1, 152.9, 150.5, 149.1, 139.3, 139.2, 139.1, 138.3, 138.1,
137.6, 137.3, 128.6, 128.5 (2 C), 128.4, 128.2, 128.1, 128.0 (2 C), 127.9,
127.8, 127.4, 127.3, 125.7, 124.4, 123.5, 114.5, 112.4, 107.0, 106.8, 103.0,
101.5, 84.5, 81.1, 79.2, 78.6, 77.4, 76.3, 76.0, 75.3, 74.9, 74.8, 74.6, 73.3,
73.1, 71.1, 70.8, 65.3, 63.8, 56.2, 56.1, 55.9; HRMS (MALDI) calcd for
C71H70O17Na [M þ Na]þ 1217.4505, found 1217.4520.
4-(20,30,40-Tri-O-benzyl-β-D-glucopyranosyloxy)benzoic
acid (39). Similar procedure as that used for 15f16 was applied
to convert trityl ether 38 into 39 (354 mg, 80%) as a white solid:
[R]25D = ꢀ20.5 (c 0.7, CHCl3); 1H NMR (400 MHz, CDCl3) δ 8.01 (d, J
= 8.8 Hz, 2 H), 7.29ꢀ7.18 (m, 15 H), 6.98 (d, J = 8.8 Hz, 2 H), 5.10 (d, J =
7.2 Hz, 1 H), 4.91 (dd, J = 4.8, 10.8 Hz, 2 H), 4.83ꢀ4.74 (m,
3 H), 4.62 (d, J = 10.8 Hz, 1 H), 3.85ꢀ3.82 (m, 1 H), 3.72ꢀ3.57 (m,
4 H), 3.49ꢀ3.48 (m, 1 H); 13C NMR (100 MHz, CDCl3) δ 170.9, 161.2,
Clemoarmanoside A (7). To a solution of 34 (30 mg, 0.026
mmol) in THF/MeOH (5 mL, v/v = 3:2) was added Pd(OH)2 (3 mg,
0.02 mmol). The reaction flask was evacuated and refilled with H2. The
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dx.doi.org/10.1021/jo200440r |J. Org. Chem. 2011, 76, 3654–3663