The Journal of Organic Chemistry
Note
3
3
2H, 2 × H−2), 5.39 (t, J3,4 = J4,5 10.2 Hz, 2H, 2 × H−4), 4.30 (dd,
(m, 2H, 2 × H−5), 2.17, 2.10, 2.09, 2.08, 2.07, 1.98 (7 × s, 7 × 6H, 14
× COCH3); 13C NMR (75 MHz, CDCl3) δ 170.4, 170.3, 170.2, 170.1,
169.8, 169.6, 169.1 (CO), 156.1, 135.7, 128.0, 117.2 (C6H4), 101.1,
98.7 (C−1 and C−1′), 76.2, 72.8, 72.7, 71.5, 70.9, 70.7, 69.1, 66.6,
62.0, 60.8 (C−2 to C−6 and C−2′ to C−6′), 20.8, 20.7, 20.6, 20.5
(COCH3); HRMS (ESI) m/z calcd. for C64H78O36 [M + Na]+
1445.4165, found 1445.4162.
3J5,6a 5.8 Hz, J6a,6b 12.6 Hz, 2H, 2 × H−6a), 4.15−4.07 (m, 4H, 2 ×
2
H−5 and H−6b), 2.22, 2.07, 2.05, 2.04 (4 × s, 4 × 6H, 8 × COCH3);
13C NMR (75 MHz, CDCl3) δ 170.5, 170.0, 169.9, 169.7 (CO)
154.9, 135.3, 127.9, 116.8 (C6H4), 95.8 (C−1), 69.3, 69.1, 68.8, 65.9,
62.1 (C−2 to C−6), 20.9, 20.7 (COCH3); HRMS (ESI) m/z calcd. for
C40H46O20 [M + K]+ 885.2214, found 885.2198.
4,4′-Bis-(4-O-[2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl]-2,3,6-
4,4′-Bis-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)biphenyl
(10).17b Yellowish solid: Rf (hexane/EtOAc 1:1) 0.19; mp 198−200
°C (lit. 199−210 °C);17b 1H NMR (300 MHz, CDCl3) δ 7.45 (d, 3JH,H
tri-O-acetyl-β-D-glucopyranosyloxy)biphenyl (15). Yellowish solid: Rf
25
(hexane/EtOAc 1:1) 0.18; mp 120−122 °C; [α]D 58.0 (c 0.2,
CHCl3); IR (KBr, cm−1) ν 3025, 1748 (CO), 1234, 1027; 1H NMR
3
8.8 Hz, 4H, 2 × HAr), 7.04 (d, JH,H 8.8 Hz, 4H, 2 × HAr), 5.35−5.25
3
(300 MHz, CDCl3) δ 7.47 (d, JH,H 8.6 Hz, 4H, 2 × HAr), 7.04 (d,
(m, 4H, 2 × H−3 and H−2), 5.21−5.14 (m, 2H, 2 × H−4), 5.12 (d,
3JH,H 8.6 Hz, 4H, 2 × HAr), 5.46 (d, 3J1′,2′ 4.1 Hz, 2H, 2 × H−1′), 5.38
3J1,2 7.7 Hz, 2H, 2 × H−1), 4.30 (dd, 3J5,6a 5.2 Hz, 2J6a,6b 12.4 Hz, 2H, 2
(dd, 3J3′,4′ 9.6 Hz, 3J2′,3′ 10.4 Hz, 2H, 2 × H−3′), 5.35 (t, 3J2,3 = 3J3,4 9.6
Hz, 2H, 2 × H−3), 5.19−5.10 (m, 4H, 2 × H−1 and 2 × H−2), 5.07
(t, 3J3′,4′ = 3J4′,5′ 9.6 Hz, 2H, 2 × H−4′), 4.88 (dd, 3J1′,2′ 4.1 Hz, 3J2′,3′ 10.4
Hz, 2H, 2 × H−2′), 4.51 (dd, 3J5,6a 2.7 Hz, 2J6a,6b 12.1 Hz, 2H, 2 × H−
6a), 4.32−4.23 (m, 4H, 2 × H−6b and 2 × H−6a′), 4.13 (t, 3J3,4 = 3J4,5
9.6 Hz, 2H, 2 × H−4), 4.07 (dd, 3J5′,6b′ 2.2 Hz, 2J6a′,6b′ 12.5 Hz, 2H, 2 ×
H−6b′), 4.05−3.96 (m, 2H, 2 × H−5), 3.92−3.88 (m, 2H, 2 × H−5′),
2.12, 2.11, 2.07, 2.06, 2.04, 2.02 (7 × s, 7 × 6H, 14 × COCH3); 13C
NMR (75 MHz, CDCl3) δ 170.5, 170.4, 170.2, 170.0, 169.6, 169.4
(CO), 156.0, 135.7, 128.0, 117.2 (C6H4), 98.4, 95.6 (C−1 and C−
1′), 75.3, 72.6, 72.3, 72.0, 70.0, 69.3, 68.6, 68.0, 62.8, 61.5 (C−2 to C−
6 and C−2′ to C−6′), 20.9, 20.8, 20.7, 20.6, 20.5 (COCH3); HRMS
(ESI) m/z calcd. for C64H78O36 [M + Na]+ 1445.4165, found
1445.4173.
3
2
× H−6a), 4.18 (dd, J5,6b 2.5 Hz, J6a,6b 12.4 Hz, 2H, 2 × H−6b),
3.91−3.85 (m, 2H, 2 × H−5), 2.07, 2.06, 2.05, 2.04 (4 × s, 4 × 6H, 8
× COCH3); 13C NMR (75 MHz, CDCl3) δ 170.5, 170.2, 169.3, 169.2
(CO), 156.1, 135.7, 127.9, 117.2 (C6H4), 99.0 (C−1), 72.6, 72.0,
71.1, 68.2, 61.9 (C−2 to C−6), 20.7, 20.6, 20.5, 20.4 (COCH3).
4,4′-Bis-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyloxy)-
biphenyl (11). Yellowish solid: Rf (hexane/EtOAc 1:1) 0.13; mp 219−
220 °C; [α]D 11.9 (c 0.2, CHCl3); IR (KBr, cm−1) ν 3025, 1743
22
1
3
(CO), 1239, 1037; H NMR (300 MHz, CDCl3) δ 7.46 (d, JH,H
3
8.2 Hz, 4H, 2 × HAr), 7.06 (d, JH,H 8.2 Hz, 4H, 2 × HAr), 5.51 (dd,
3J1,2 8.0 Hz, 3J2,3 10.4 Hz, 2H, 2 × H−2), 5.48 (dd, 3J4,5 1.1 Hz, 3J3,4 3.3
3
3
Hz, 2H, 2 × H−4), 5.13 (dd, J3,4 3.3, J2,3 10.4 Hz, 2H, 2 × H−3),
5.08 (d, 3J1,2 8.0 Hz, 2H, 2 × H−1), 4.26 (dd, 3J5,6a 6.9 Hz, 2J6a,6b 11.2
Hz, 2H, 2 × H−6a), 4.16 (dd, 3J5,6b 6.0 Hz, 2J6a,6b 11.2 Hz, 2H, 2 × H−
6b), 4.09 (ddd, 3J4,5 1.1 Hz, 3J5,6b 6.0 Hz, 3J5,6a 6.9 Hz, 2H, 2 × H−5),
2.20, 2.18, 2.09, 2.07 (4 × s, 4 × 6H, 8 × COCH3); 13C NMR (75
MHz, CDCl3) δ 170.4, 170.2, 170.1, 169.4 (CO) 156.3, 135.7,
128.0, 117.2 (C6H4), 99.7 (C−1), 71.0, 70.8, 68.6, 66.8, 61.3 (C−2 to
C−6), 20.7. 20.6, 20.5 (COCH3); HRMS (ESI) m/z calcd. for
C40H46O20 [M + Na]+ 869.2475, found 869.2471.
4,4′-Bis-(6-O-[2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl]-2,3,6-
tri-O-acetyl-β-D-glucopyranosyloxy)biphenyl (16). Yellowish solid: Rf
25
(hexane/EtOAc 4:6) 0.21; mp 118−120 °C; [α]D 85.6 (c 0.14,
CHCl3); IR (KBr, cm−1) ν 3026, 1746 (CO), 1236, 1025; 1H NMR
3
(300 MHz, CDCl3) δ 7.60 (d, JH,H 8.6 Hz, 4H, 2 × HAr), 7.03 (d,
3JH,H 8.6 Hz, 4H, 2 × HAr), 5.40 (dd, 3J3′,4′ 3.5 Hz, 3J2′,3′ 10.0 Hz, 2H, 2
× H−3′), 5.35−5.05 (m, 14H, 2 × H−1, H−2, H−3, H−4, H−1′, H−
2′ and H−4′), 4.20 (t, 3J5′,6a′ = 3J5′,6b′ 6.5 Hz, 2H, 2 × H−5′), 3.97−3.76
4,4′-Bis-(2,3,4-tri-O-acetyl-β-D-xylopyranosyloxy)biphenyl (12).
Yellowish solid: Rf (hexane/EtOAc 1:1) 0.38; mp 174−176 °C;
[α]D24 −25.1 (c 0.24, CHCl3); IR (KBr, cm−1) ν 3035, 1741 (CO),
1247, 1033; 1H NMR (300 MHz, CDCl3) δ 7.47 (d, 3JH,H 8.6 Hz, 4H,
2 × HAr), 7.06 (d, 3JH,H 8.6 Hz, 4H, 2 × HAr), 5.30−5.16 (m, 6H, 2 ×
3
(m, 8H, 2 × H−5, H−6a, H−6a′ and H−6b′), 3.60 (dd, J5,6b 1.4 Hz,
2J6a,6b 10.1 Hz, 2H, 2 × H−6b), 2.12, 2.10, 2.08, 2.07, 2.05, 2.01, 1.92
(7 × s, 7 × 6H, 14 × COCH3); 13C NMR (75 MHz, CDCl3) δ 170.5,
170.3, 170.2, 170.0, 169.8, 169.4, 169.3 (CO), 155.9, 135.7, 128.2,
116.7 (C6H4), 98.4, 96.2 (C−1 and C−1′), 72.9, 72.7, 71.1, 68.7, 68.1,
68.0, 67.3, 66.4, 66.3, 61.5 (C−2 to C−6 and C−2′ to C−6′), 20.8,
20.7, 20.6, 20.5, 20.4 (COCH3); HRMS (ESI) m/z calcd. for
C64H78O36 [M + Na]+ 1445.4165, found 1445.4160.
3
3
3
H−1 and H−2 and H−3), 5.03 (td, J4,5a 4.7 Hz, J3,4 = J4,5b 7.7 Hz,
2H, 2 × H−4), 4.25 (dd, 3J4,5a 4.7 Hz, 2J5a,5b 12.1 Hz, 2H, 2 × H−5a),
3.55 (dd, 3J4,5b 7.7 Hz, 2J5a,5b 12.1 Hz, 2H, 2 × H−5b), 2.10, 2.09 (3 ×
s, 3 × 6H, 6 × COCH3); 13C NMR (75 MHz, CDCl3) δ 169.9, 169.8,
169.4 (CO) 155.9, 135.5, 128.0, 117.1 (C6H4), 98.5 (C−1), 70.7,
70.1, 68.5, 61.9 (C−2 to C−5), 20.8, 20.7, 20.6 (COCH3); HRMS
(ESI) m/z calcd. for C34H38O16 [M + Na]+ 725.2052, found 725.2044.
4,4′-Bis-(2,3,4-tri-O-acetyl-α-D-xylopyranosyloxy)biphenyl (13).
3,3′-Bis-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyloxy)biphenyl
(19). Yellowish solid: Rf (hexane/EtOAc 55:45) 0.24; decomposed
over 160 °C; [α]D23 64.7 (c 0.2, CHCl3); IR (KBr, cm−1) ν 3027, 1751
(CO), 1238, 1025; 1H NMR (300 MHz, CDCl3) δ 7.38 (t, 3JH,H 7.9
Hz, 2H, 2 × HAr), 7.34−7.28 (m, 4H, 4 × HAr), 7.09 (dt, 4JH,H 1.3 Hz,
24
Yellowish solid: Rf (hexane/EtOAc 1:1) 0.19; mp 84−86 °C; [α]D
157.5 (c 0.21, CHCl3); IR (KBr, cm−1) ν 3028, 1748 (CO), 1235,
3
3JH,H 7.9 Hz, 2H, 2 × HAr), 5.62 (d, J1,2 2.2 Hz, 2H, 2 × H−1), 5.60
1
3
1028; H NMR (300 MHz, CDCl3) δ 7.48 (d, JH,H 8.5 Hz, 4H, 2 ×
(dd, 3J2,3 3.3 Hz, 3J3,4 9.9 Hz, 2H, 2 × H−3), 5.48 (dd, 3J1,2 2.2 Hz, 3J2,3
3.3 Hz, 2H, 2 × H−2), 5.39 (t, 3J3,4 = 3J4,5 9.9 Hz, 2H, 2 × H−4), 4.30
(dd, 3J5,6a 5.2 Hz, 2J6a,6b 12.0 Hz, 2H, 2 × H−6a), 4.17−4.10 (m, 2H, 2
× H−5), 4.07 (dd, 3J5,6b 1.9 Hz, 2J6a,6b 12.0 Hz, 2H, 2 × H−6b), 2.22,
2.07, 2.05, 1.97 (4 × s, 4 × 6H, 8 × COCH3); 13C NMR (75 MHz,
CDCl3) δ 170.5, 170.0, 169.9, 169.8 (CO), 156.0, 142.2, 130.0,
121.8, 115.5, 115.3 (C6H4), 95.8 (C−1), 69.4, 69.2, 68.9, 65.9, 62.1
(C−2 to C−6), 20.9, 20.7, 20.5 (COCH3); HRMS (ESI) m/z calcd.
for C40H46O20 [M + Na]+ 869.2475, found 869.2466.
HAr), 7.13 (d, 3JH,H 8.5 Hz, 4H, 2 × HAr), 5.74 (d, 3J1,2 3.1 Hz, 2H, 2 ×
3
3
3
H−1), 5.73 (t, J2,3 = J3,4 10.6 Hz, 2H, 2 × H−3), 5.08 (td, J4,5a 6.1
3
3
3
3
Hz, J3,4 = J4,5b 10.6 Hz, 2H, 2 × H−4), 5.00 (dd, J1,2 3.1 Hz, J2,3
10.6 Hz, 2H, 2 × H−2), 3.93 (dd, 3J4,5a 6.1 Hz, 2J5a,5b 10.6 Hz, 2H, 2 ×
H−5a), 3.74 (t, 3J4,5b = 2J5a,5b 11.0 Hz, 2H, 2 × H−5b), 2.09, 2.08, 2.06
(3× s, 3 × 6H, 6 × COCH3); 13C NMR (75 MHz, CDCl3) δ 170.3,
170.1, 170.0 (CO), 155.4, 135.2, 128.0, 116.8 (C6H4), 94.2 (C−1),
70.6, 69.4, 69.1, 59.0 (C−2 to C−5), 20.8, 20.7 (COCH3); HRMS
(ESI) m/z calcd. for C34H38O16 [M + Na]+ 725.2052, found 725.2039.
4,4′-Bis-(4-O-[2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl]-2,3,6-
tri-O-acetyl-β-D-glucopyranosyloxy)biphenyl (14). Yellowish solid: Rf
2,2′-Bis-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyloxy)biphenyl
(20). Yellowish solid: Rf (hexane/EtOAc 1:1) 0.26; decomposed over
23
160 °C; [α]D 20.7 (c 0.2, CHCl3); IR (KBr, cm−1) ν 3027, 1745
25
(hexane/EtOAc 4:6) 0.21; mp 130−132 °C; [α]D −8.3 (c 0.33,
4
(CO), 1243, 1028;1H NMR (300 MHz, CDCl3) δ 7.39 (td, JH,H
CHCl3); IR (KBr, cm−1) ν 3030, 1743 (CO), 1242, 1025; 1H NMR
1.7 Hz, 3JH,H 7.1 Hz, 2H, 2 × HAr), 7.36−7.28 (m, 4H, 2 × HAr), 7.18
(td, 4JH,H 1.1 Hz, 3JH,H 7.1 Hz, 2H, 2 × HAr), 5.68 (d, 3J1,2 1.9 Hz, 2H,
3
(300 MHz, CDCl3) δ 7.45 (d, JH,H 8.8 Hz, 4H, 2 × HAr), 7.03 (d,
3JH,H 8.8 Hz, 4H, 2 × HAr), 5.36 (d, 3J3′,4′ 3.3 Hz, 2H, 2 × H−4′), 5.31
3
3
(t, 3J2,3 = 3J3,4 8.8 Hz, 2H, 2 × H−3), 5.21 (dd, 3J1,2 7.8 Hz, 3J2,3 8.8 Hz,
2 × H−1), 5.32 (dd, J1,2 1.9 Hz, J2,3 3.3 Hz, 2H, 2 × H−2), 5.19 (t,
3J3,4 = 3J4,5 10.2 Hz, 2H, 2 × H−4), 4.90 (dd, 3J2,3 3.3 Hz, 3J3,4 10.2 Hz,
2H, 2 × H−3), 4.11 (dd, 3J5,6a 5.2 Hz, 2J6a,6b 12.2 Hz, 2H, 2 × H−6a),
3.92 (dd, 3J5,6b 1.9 Hz, 2J6a,6b 12.2 Hz, 2H, 2 × H−6b), 3.61−3.57 (m,
2H, 2 × H−5), 2.14, 2.01, 1.96, 1.92 (4 × s, 4 × 6H, 8 × COCH3);
13C NMR (75 MHz, CDCl3) δ 170.6, 169.9, 169.6 (CO), 153.1,
3
3
2H, 2 × H−2), 5.12 (dd, J1′,2′ 8.0 Hz, J2′,3′ 10.4 Hz, 2H, 2 × H−2′),
3
3
3
5.09 (d, J1,2 7.5 Hz, 2H, 2 × H−1), 4.98 (dd, J3′,4′ 3.3 Hz, J2′,3′ 10.4
Hz, 2H, 2 × H−3′), 4.53−4.52 (m, 2H, 2 × H−6a), 4.52 (d, 3J1′,2′ 7.8
Hz, 2H, 2 × H−1′), 4.20−4.05 (m, 6H, 2 × H−6b, 2 × H−6a′ and 2 ×
H−6b′), 3.92 (m, 2H, 2 × H−5′), 3.89 (m, 2H, 2 × H−4), 3.83−3.78
2975
dx.doi.org/10.1021/jo2025652 | J. Org. Chem. 2012, 77, 2971−2977