Ding et al.
JOCArticle
21.1; MS (EI-LR) 427 (Mþ); HRMS (EI) calcd for C26H21NO5
(Mþ) 427.1420, found 427.1423.
21.1, 20.0; MS (EI-LR) 377 (Mþ); HRMS (EI) calcd for
C22H19NO5 (Mþ) 377.1263, found 377.1255.
O-Acetyl-D-xylosides 49 and 50: reddish solid (74%); 1H
NMR (300 MHz, CDCl3) δ 9.89 (d, 1H, J = 4.5 Hz, for 50),
9.83 (d, 1H, J = 3.3 Hz, for 49), 9.55 (d, 1H, J = 9.0 Hz, for 50),
9.54 (d, 1H, J = 8.7 Hz, for 49), 8.33 (d, 1H, J = 8.4 Hz, for 50),
8.32 (d, 1H, J = 8.4 Hz, for 49), 8.06 (d, 2H, J = 9.0 Hz), 7.64 (s,
2H), 7.53 (m, 6H), 5.01 (m, 1H), 4.84 (s, 1H), 4.80 (br s, 1H), 4.69
(br s, 1H), 4.08 (br s, 1H), 4.03 (br s, 1H), 3.80 (m, 2H), 3.54 (d,
1H, J = 12.9 Hz), 3.20 (t, 1H, J = 11.1 Hz), 2.62 (d, 1H, J =
12.6 Hz, for 50), 2.53 (s, 6H), 2.34 (d, 1H, J = 13.2 Hz, for 49),
2.18 (s, 3H, for 50), 2.12 (s, 3H, for 49), 2.00 (m, 1H, for 49), 1.68
(d, 1H, J = 12.9 Hz, for 50); 13C NMR (75 MHz, CDCl3) δ
186.3, 186.2, 185.6, 185.5, 170.3, 170.2, 148.8, 147.7, 138.6,
136.7, 136.6, 136.5, 136.4, 136.1, 134.6, 134.5, 134.4, 134.3,
132.0, 128.7, 128.4, 128.2, 127.6, 126.3, 125.9, 122.3, 115.9,
115.7, 111.7, 111.4, 71.1, 69.9, 68.3, 67.6, 61.0, 59.2, 46.1, 44.6,
27.3, 23.6, 21.5, 21.2, 21.1; MS (EI-LR) 427 (Mþ); HRMS (EI)
calcd for C26H21NO5 (Mþ) 427.1420, found 427.1416.
O-Acetyl-L-rhamnoside 61: bright orange solid (65%), mp
181-183 °C; 1H NMR (300 MHz, CDCl3) δ 8.37 (s, 1H), 8.30
(s, 1H), 7.98 (m, 2H), 7.46 (m, 3H), 7.00 (d, 1H, J=8.4 Hz), 5.71
(d, 1H, J=3.0 Hz), 5.31 (br s, 1H), 4.82 (dd, 1H, J=4.2, 9.9 Hz),
3.65 (dq, 1H, J=6.3, 9.6 Hz), 3.50 (br s, 1H), 2.39 (d, 1H, J=12.9
Hz), 2.09 (s, 3H), 2.03 (m, 1H), 1.13 (d, 3H, J=6.3 Hz); 13C
NMR (75 MHz, CDCl3) δ 170.5, 137.5, 131.8, 131.4, 130.9,
128.4, 128.3, 127.8, 126.7, 125.5, 125.3, 121.3, 118.1, 117.5,
112.9, 77.4, 75.7, 65.3, 34.4, 28.4, 21.1, 17.8; MS (EI-LR) 347
(Mþ); HRMS (EI) calcd for C22H21NO3 (Mþ) 347.1521, found
347.1521.
General Procedure for Deacetylation of the C- and N-Glyco-
sidation Products. Each glycosidation cycloadduct prepared
above was dissolved in a solution of NH3 H2O/MeOH (1:4)
3
and stirred at rt overnight. After completion of the reaction as
indicated by TLC, the reaction mixture was diluted with water
and extracted with CH2Cl2 (2 ꢀ 10 mL). The combined organic
layers were dried over anhydrous Na2SO4, concentrated in
vacuo, and purified by column chromatography on silica gel
(CH2Cl2/MeOH, 40:1) to afford the corresponding deacetylated
cycloadduct.
Penta-O-acetyl-D-lactoside 53: reddish solid (44%), mp 136-
D
1
138 °C; [R]20 -406 (c 0.064, CHCl3); H NMR (300 MHz,
CDCl3) δ 9.90 (d, 1H, J = 3.6 Hz), 9.55 (d, 1H, J = 9.3 Hz), 8.34
(d, 1H, J = 9.0 Hz), 8.07 (d, 1H, J = 9.0 Hz), 7.66 (s, 1H), 7.56
(d, 2H, J = 7.5 Hz), 7.47 (d, 1H, J = 7.5 Hz), 5.47 (br s, 1H), 5.29
(m, 1H), 5.05 (m, 1H), 4.85 (br s, 1H), 4.67 (d, 1H, J = 7.8 Hz),
4.52 (d, 1H, J = 6.6 Hz), 4.34 (d, 1H, J = 6.3 Hz), 4.19 (m, 1H),
4.03 (m, 2H), 3.71 (d, 1H, J = 3.0, 9.9 Hz), 3.49 (m, 1H), 2.54 (s,
3H), 2.28 (s, 4H), 2.02 (m, 13H); 13C NMR (75 MHz, CDCl3) δ
186.5, 185.0, 170.6, 170.5, 170.4, 170.1, 169.2, 148.3, 138.4,
136.8, 136.4, 136.0, 134.8, 134.4, 131.9, 128.6, 128.4, 128.2,
127.6, 125.9, 122.5, 115.3, 111.8, 101.4, 78.9, 70.9, 70.8, 68.6,
68.4, 68.3, 66.9, 63.2, 61.9, 47.1, 27.1, 21.5, 20.9, 20.8, 20.7, 20.5,
20.4; MS (EI-LR) 787 (Mþ); HRMS (EI) calcd for C41H41NO15
(Mþ) 787.2476, found 787.2454.
Angucycline 30: reddish solid (90%), [R]20 þ553 (c 0.038,
D
THF); mp 232-235 °C dec; 1H NMR (300 MHz, CDCl3) δ 9.83
(d, 1H, J = 4.8 Hz), 9.52 (d, 1H, J=9.3 Hz), 8.27 (d, 1H, J = 9.3
Hz), 8.04 (d, 1H, J = 8.4 Hz), 7.64 (s, 1H), 7.54 (m, 3H), 4.79 (br
s, 1H), 3.94 (br s, 1H), 3.41 (dt, 1H, J=3.0, 9.6 Hz), 3.21 (dq, 1H,
J = 9.6, 6.0 Hz), 2.54 (s, 3H), 2.28 (d, 1H, J = 13.2 Hz), 2.01 (m,
2H), 1.26 (d, 3H, J = 6.3 Hz); 13C NMR (75 MHz, CDCl3) δ
186.3, 185.6, 148.7, 138.7, 136.5, 136.2, 134.6, 134.4, 132.0,
128.7, 128.5, 128.2, 127.8, 127.7, 122.3, 115.9, 111.7, 75.1,
68.8, 68.3, 49.0, 27.9, 21.6, 18.1; MS (EI-LR) 399 (Mþ); HRMS
(EI) calcd for C25H21NO4 (Mþ) 399.1471, found 399.1477.
Penta-O-acetyl-D-lactoside 54: reddish solid (34%), mp 130-
D
Angucycline 31: reddish solid (92%), [R]20 -1500 (c 0.036,
D
1
1
133 °C; [R]20 þ717 (c 0.046, CHCl3); H NMR (300 MHz,
CHCl3/CH3OH=1:1); mp 204-206 °C; H NMR (300 MHz,
CDCl3) δ 10.06 (d, 1H, J = 4.8 Hz), 9.55 (d, 1H, J = 8.7 Hz),
8.31 (d, 1H, J = 8.4 Hz), 8.07 (d, 1H, J = 8.7 Hz), 7.65 (s, 1H),
7.55 (m, 2H), 7.46 (d, 1H, J = 7.8 Hz), 5.46 (d, 1H, J = 3.3 Hz),
5.27 (m, 1H), 5.03 (m, 2H), 4.61 (d, 1H, J = 8.1 Hz), 4.33 (m,
2H), 4.23 (br s, 1H), 4.08 (m, 2H), 3.74 (m, 2H), 3.61 (d, 1H, J =
5.1 Hz), 2.62 (d, 1H, J = 13.2 Hz), 2.54 (s, 3H), 2.20 (s, 6H), 2.09
(s, 3H), 2.00 (s, 6H), 1.71 (dd, 1H, J = 3.6, 14.1 Hz); 13C NMR
(75 MHz, CDCl3) δ 186.2, 185.6, 170.7, 170.6, 170.2, 170.0,
169.7, 145.3, 138.6, 136.4, 136.3, 134.6, 134.4, 134.2, 132.0,
129.7, 128.8, 128.4, 128.2, 127.6, 122.2, 115.8, 112.0, 102.3,
81.8, 71.2, 70.6, 68.6, 67.6, 67.0, 64.5, 61.6, 47.6, 21.5, 21.3,
20.8, 20.7, 20.6, 20.5; MS (EI-LR) 787(Mþ); HRMS (EI) calcd
for C41H41NO15 (Mþ) 787.2476, found 787.2476.
CDCl3) δ 10.10 (d, 1H, J = 4.8 Hz), 9.58 (d, 1H, J = 9.0 Hz),
8.36 (d, 1H, J = 9.0 Hz), 8. 09 (d, 1H, J = 8.7 Hz), 7.67 (s, 1H),
7.57 (d, 2H, J = 7.5 Hz), 7.45 (d, 1H, J = 7.5 Hz), 4.96 (d, 1H,
J = 4.2 Hz), 3.86 (br s, 1H), 3.61 (m, 2H), 2.65 (m, 1H), 2.55 (s,
3H), 2.05 (br s, 1H), 1.72 (dd, 1H, J = 3.9, 13.5 Hz), 1.16 (d, 3H,
J = 6.3 Hz); 13C NMR (75 MHz, CD3OD) δ 187.8, 186.2, 146.5,
139.6, 137.4, 137.0, 135.8, 135.4, 134.2, 132.9, 131.8, 129.7,
129.4, 128.9, 128.6, 123.1, 116.4, 112.5, 78.6, 69.1, 68.9, 50.9,
22.1, 21.7, 20.3; MS (EI-LR) 339 (Mþ); HRMS (EI) calcd for
C25H21NO4 (Mþ) 399.1471, found 399.1478.
Angucycline 39: reddish solid (96%), [R]20 -750 (c 0.024,
D
CH3CN); mp 211-214 °C dec; 1H NMR (300 MHz, CD3OD) δ
9.86 (d, 1H, J = 4.2 Hz), 9.48 (d, 1H, J = 9.0 Hz), 8.28 (d, 1H,
J = 8.7 Hz), 8.05 (d, 1H, J = 8.7 Hz), 7.65 (s, 3H), 7.50 (m, 3 H),
4.82 (br s, 1H), 3.96 (br s, 1H), 3.74 (m, 3H), 3.22 (dt, 1H, J = 9.9,
3.9Hz), 2.54 (s, 3H), 2.27 (d, 1H, J = 12.9 Hz), 2.01 (ddd, 1H, J =
1.8, 4.8, 13.2 Hz); 13C NMR (75 MHz, CD3OD) δ 186.4, 185.1,
148.5, 138.4, 136.3, 136.2, 135.8, 134.5, 134.3, 131.8, 128.4, 128.2,
127.8, 127.5, 127.0, 122.1, 115.4, 111.1, 72.3, 68.9, 68.2, 61.9, 48.8,
27.2, 21.2; MS (EI-LR) 415 (Mþ); HRMS (EI) calcd for
C25H21NO5 (Mþ) 415.1420, found 415.1433.
O-Acetyl-L-rhamnoside 56: reddish solid (54%), mp
1
155-158 °C; H NMR (300 MHz, CDCl3) δ 9.97 (d, 1H, J=
3.3 Hz), 8.27 (m, 2H), 7.76 (m, 2H), 7.62 (d, 1H, J=7.5 Hz), 7.50
(d, 1H, J=7.5 Hz), 4.81 (s, 1H), 4.65 (dd, 1H, J=3.0, 9.9 Hz), 4.07
(s, 1H), 3.47 (dq, 1H, J = 6.0, 9.6 Hz), 2.35 (d, 1H, J=13.5 Hz),
2.16 (s, 3H), 1.98 (ddd, 1H, J =1.5, 4.5, 13.2 Hz), 1.12 (d, 3H, J=
6.3 Hz); 13C NMR (75 MHz, CDCl3) δ 185.2, 183.4, 170.4, 149.4,
136.1, 134.8, 134.0, 133.2, 132.9, 127.9, 126.8, 126.7, 115.7, 112.2,
76.7, 68.3, 65.5, 46.4, 27.5, 21.2, 17.9; MS (EI-LR) 377 (Mþ);
HRMS (EI) calcd for C22H19NO5 (Mþ) 377.1263, found
377.1257.
Angucycline 40: reddish solid (94%), [R]20 þ1765 (c 0.017,
D
MeOH/CH3CN=1:10); mp 176-178 °C; 1H NMR (300 MHz,
CD3OD) δ 10.04 (d, 1H, J=5.1 Hz), 9.51 (d, 1H, J=9.0 Hz), 8.30
(d, 1H, J=7.8 Hz), 8.07 (d, 1H, J=8.4 Hz), 7.65 (s, 1H), 7.49 (m,
3H), 5.00 (br s, 1H), 3.86 (br s, 1H), 3.73 (d, 1H, J=5.7 Hz), 3.55
(m, 4H), 3.30 (m, 1H), 2.66 (d, 1H, J=13.8 Hz), 2.54 (s, 3H), 1.73
(dd, 1H, J=3.3, 13.2 Hz); 13C NMR (75 MHz, CD3OD) δ 186.5,
185.3, 145.4, 138.5, 136.3, 136.1, 134.6, 134.3, 133.4, 131.9,
130.1, 128.6, 128.3, 127.9, 127.5, 122.0, 115.3, 111.5, 72.7,
72.5, 67.7, 63.0, 48.3, 21.3, 20.9; MS (EI-LR) 415 (Mþ); HRMS
(EI) calcd for C25H21NO5 (Mþ) 415.1420, found 415.1430.
O-Acetyl-L-rhamnoside 57: reddish solid (26%), mp 152-
1
154 °C; H NMR (300 MHz, CDCl3) δ 10.23 (d, 1H, J=4.8
Hz), 8.25 (m, 2H), 7.73 (m, 2H), 7.60 (d, 1H, J=7.5 Hz), 7.47 (d,
1H, J=7.5 Hz), 4.94 (d, 1H, J=4.2 Hz), 4.63 (d, 1H, J=5.4 Hz),
3.84 (m, 2H), 2.58 (d, 1H, J=13.5 Hz), 2.15 (s, 3H), 1.70 (m, 1H),
1.06 (d, 3H, J=6.6 Hz); 13C NMR (75 MHz, CDCl3) δ 185.1,
183.4, 170.2, 146.6, 134.7, 134.6, 134.1, 133.9, 133.1, 133.0,
131.0, 126.8, 126.7, 115.7, 112.8, 77.5, 67.4, 66.8, 46.6, 21.7,
6118 J. Org. Chem. Vol. 74, No. 16, 2009