F. S. Ekholm et al. / Carbohydrate Research 346 (2011) 858–862
861
0
0
1H, 11-OH), 8.29–6.90 (m, 24 H, arom. H), 6.02 (dd, 1H, J3 ,4 = 9.5,
1.2.6. 7-O-(
a
-
D
-Mannopyranosyl)-4-deoxy-
e
-rhodomycinone (7)
J3 ,2 = 10.0 Hz, H-30), 5.72 (dd, 1H, J4 ,5 = 10.0 Hz, H-40), 5.56 (d,
Synthesized from 6 (107 mg (containing impurities), 0.1 mmol)
according to the general procedure for deprotection providing 7
as a red solid (37 mg, 86% (over two steps)). Rf = 0.16 (in MeOH/
CH2Cl2 1:10). 1H NMR (600.13 MHz, CD3OD + CDCl3): d 8.37–7.85
(m, 4 H, arom. H), 5.53 (dd, 1H, J7,8a = 1.8, J7,8b = 3.9 Hz, H-7), 5.28
0
0
0
0
1H, J1 ,2 = 8.0 Hz, H-10), 5.45 (dd, 1H, H-20), 5.34 (dd, 1H, J7,8a
=
0
0
0
0
0
0
1.8, J7,8b = 4.2 Hz, H-7), 4.76 (dd, 1H, J6 a,5 = 3.1, J6 a,6 b = ꢁ12.1 Hz,
H-60a), 4.58 (dd, 1H, J6 b,5 = 5.0 Hz, H-60b), 4.32 (d, 1H, J10,8a
=
0
0
ꢁ1.2 Hz, H-10), 4.30 (ddd, 1H, H-50), 3.67 (s, 3 H, 10-COOCH3),
2.55 (ddd, 1H, J8a,8b = ꢁ15.0 Hz, H-8a), 2.20 (dd, 1H, H-8b), 1.73
(dq, 1H, J13a,14 = 7.3, J13a,13b = ꢁ13.9 Hz, H-13a), 1.45 (dq, 1H,
J13b,14 = 7.3 Hz, H-13b), 1.10 (dd, 1H, H-14).
(d, 1H, J1 ,2 = 1.7 Hz, H-10), 4.34 (d, 1H, J10,8a = ꢁ1.1 Hz, H-10), 4.14
0
0
(ddd, 1H, J5 ,6 a = 2.9, J5 ,6 b = 3.3, J5 ,4 = 10.0 Hz, H-50), 3.94 (dd,
0
0
0
0
0
0
1H, J6 a,6 b = ꢁ12.1 Hz, H-60a), 3.93 (dd, 1H, H-60b), 3.82 (dd, 1H,
0
0
13C NMR (150.90 MHz, CDCl3): d 186.7 (C-5), 186.2 (C-12), 171.7
(10-COOCH3), 166.3 (60-OCOPh), 165.8 (30-OCOPh), 165.3 (40-
OCOPh), 165.2 (20-OCOPh), 156.3 (C-6), 156.1 (C-11), 135.2–128.1
(arom. C), 111.7 (C-11a), 111.2 (C-5a), 103.1 (C-10), 72.5 (C-50),
72.4 (C-30), 72.1 (C-20), 71.8 (C-7), 70.8 (C-9), 69.8 (C-40), 63.0 (C-
60), 52.4 (10-COOCH3), 51.4 (C-10), 34.7 (C-8), 32.8 (C-13), 6.8 (C-
14).
J4 ,3 = 9.5, Hz, H-40), 3.81 (dd, 1H, J2 ,3 = 3.3 Hz, H-20), 3.72 (s, 3 H,
10-COOCH3), 3.68 (dd, 1H, H-30), 2.48 (ddd, 1H, J8a,8b = ꢁ15.3 Hz,
0
0
0
0
H-8a), 2.07 (dd, 1H, H-8b), 1.79 (dq, 1H, J13a,14 = 7.3, J13a,13b
=
ꢁ14.1 Hz, H-13a), 1.54 (dq, 1H, J13b,14 = 7.3 Hz, H-13b), 1.15 (dd,
1H, H-14).
13C NMR (150.90 MHz, CD3OD + CDCl3): d 186.7 (C-5), 186.4 (C-
12), 171.3 (10-COOCH3), 156.1 (C-6), 155.3 (C-11), 135.1–126.6
(arom. C), 111.8 (C-11a), 111.3 (C-5a), 97.0 (C-10), 73.4 (C-50),
70.8 (C-30), 70.7 (C-20), 70.5 (C-9), 66.3 (C-40), 65.3 (C-7), 60.9 (C-
60), 51.9 (10-COOCH3), 51.6 (C-10), 32.2 (C-13), 29.1 (C-8), 6.0 (C-
14).
HRMS: calcd for C56H46O17Na1 [M+Na]+ 1013.2633; found
1013.2668.
1.2.4. 7-O-(b-D-Glucopyranosyl)-4-deoxy-e-rhodomycinone (4)
HRMS: calcd for
597.1588.
C
28H30O13Na1 [M+Na]+ 597.1584; found
Synthesized from 3 (91 mg, 0.09 mmol) according to the general
procedure for deprotection providing 4 as a red solid (51 mg,
97%). Rf = 0.14 (in MeOH/CH2Cl2 1:10). 1H NMR (600.13 MHz,
CD3OD + CDCl3): d 8.20–7.75 (m, 4 H, arom. H), 5.29 (dd, 1H,
1.2.7. 7-O -(20,30,40,60-Tetra-O-benzoyl-
deoxy- -rhodomycinone (9)
Synthesized from (25 mg, 0.06 mmol) and
a-L-rhamnopyranosyl)-4-
e
J7,8a = 1.7, J7,8b = 4.5 Hz, H-7), 4.91 (d, 1H, J1 ,2 = 7.8 Hz, H-10), 4.24
0
0
1
8 (41 mg,
0
0
0
0
(d, 1H, J10,8a = ꢁ1.2 Hz, H-10), 3.93 (dd, 1H, J6 a,5 = 2.2, J6 a,6 b
=
0.067 mmol) according to the general procedure for glycosylation
providing 9 as an orange solid (containing 10% of hydrolyzed do-
nor) (68 mg). Rf = 0.74 (in hexane/EtOAc 1:1)
(600.13 MHz, CDCl3): d 13.53 (s, 1H, 6-OH), 13.37 (s, 1H, 11-OH),
ꢁ11.8 Hz, H-60a), 3.79 (dd, 1H, J6 b,5 = 5.1 Hz, H-60b), 3.70 (s, 3 H,
0
0
10-COOCH3), 3.47 (dd, 1H, J3 ,4 = 8.9, J3 ,2 = 9.3 Hz, H-30), 3.43
0
0
0
0
.
1H NMR
(ddd, 1H, J5 ,4 = 9.8 Hz, H-50), 3.39 (dd, 1H, H-40), 3.22 (dd, 1H,
H-20), 2.66 (ddd, 1H, J8a,8b = ꢁ15.1 Hz, H-8a), 2.22 (dd, 1H, H-8b),
1.71 (dq, 1H, J13a,14 = 7.3, J13a,13b = ꢁ14.0 Hz, H-13a), 1.57 (dq, 1H,
J13b,14 = 7.3 Hz, H-13b), 1.15 (dd, 1H, H-14).
0
0
0
0
0
0
8.36–7.17 (m, 19 H, arom. H), 5.82 (dd, 1H, J2 ,1 = 1.9, J2 ,3 = 3.4 Hz,
H-20), 5.73 (dd, 1H, J4 ,5 = 9.8, J4 ,3 = 10.1 Hz, H-40), 5.65 (d, 1H, H-
0
0
0
0
10), 5.64 (dd, 1H, H-30), 5.40 (dd, 1H, J7,8a = 1.7, J7,8b = 4.4 Hz, H-7),
13C NMR (150.90 MHz, CD3OD + CDCl3): d 188.1 (C-5), 187.9 (C-
12), 172.8 (10-COOCH3), 157.8 (C-6), 156.8 (C-11), 137.6–127.9
(arom. C), 112.9 (C-11a), 112.6 (C-5a), 106.2 (C-10), 78.1 (C-50),
77.7 (C-30), 75.5 (C-20), 72.3 (C-7), 71.9 (C-9), 71.3 (C-40), 62.5 (C-
60), 52.8 (10-COOCH3), 52.0 (C-10), 36.2 (C-8), 34.1 (C-13), 7.2 (C-
14).
4.45 (dq, 1H, J5 ,6 = 6.2 Hz, H-50), 4.40 (d, 1H, J10,8a = ꢁ1.2 Hz,
H-10), 3.75 (s, 3 H, 10-COOCH3), 2.50 (ddd, 1H, J8a,8b = ꢁ15.0 Hz,
0
0
H-8a), 2.36 (dd, 1H, H-8b), 1.92 (dq, 1H, J13a,14 = 7.3, J13a,13b
=
ꢁ14.0 Hz, H-13a), 1.54 (dq, 1H, J13b,14 = 7.3 Hz, H-13b), 1.45 (d,
1H, H-60), 1.20 (dd, 1H, H-14).
13C NMR (150.90 MHz, CDCl3): d 187.1 (C-12), 186.7 (C-5), 171.5
(10-COOCH3), 165.9 (40-OCOPh), 165.4 (20-OCOPh, 30-OCOPh),
156.8 (C-6), 156.1 (C-11), 134.6–127.2 (arom. C), 112.3 (C-11a),
111.9 (C-5a), 101.5 (C-10), 72.8 (C-7), 71.6 (C-40), 71.1 (C-9), 70.6
(C-20), 70.0 (C-30), 68.1 (C-50), 52.6 (10-COOCH3), 52.0 (C-10), 33.8
(C-8), 32.4 (C-13), 17.7 (C-60), 6.9 (C-14).
HRMS: calcd for
597.1588.
C
28H30O13Na1 [M+Na]+ 597.1584; found
1.2.5. 7-O -(20,30,40,60-Tetra-O-benzoyl-
deoxy- -rhodomycinone (6)
Synthesized from (31 mg, 0.074 mmol) and
a-D-mannopyranosyl)-4-
e
HRMS: calcd for
893.2400.
C
49H42O15Na1 [M+Na]+ 893.2421; found
1
5 (61 mg,
0.081 mmol) according to the general procedure for glycosylation
providing 6 as an orange solid (containing 10% of hydrolyzed do-
nor) (107 mg). Rf = 0.58 (in hexane/EtOAc 1:1)
.
1H NMR
1.2.8. 7-O-(
L-Rhamnopyranosyl)-4-deoxy-e-rhodomycinone (10)
(600.13 MHz, CDCl3): d 13.80 (s, 1H, 6-OH), 13.40 (s, 1H, 11-OH),
Synthesized from
9
(65 mg (containing impurities),
0
0
8.40–7.21 (m, 24 H, arom. H), 6.23 (dd, 1H, J4 ,3 = 10.1,
0.074 mmol) according to the general procedure for deprotection
providing 10 as a red solid (30 mg, 90% over two steps). Rf = 0.45
(in EtOAc). 1H NMR (600.13 MHz, CD3OD + CDCl3): d 8.30–7.82
J4 ,5 = 10.2 Hz, H-40), 5.82 (dd, 1H, J3 ,2 = 3.2 Hz, H-30), 5.64 (d, 1H,
0
0
0
0
J1 ,2 = 1.9 Hz, H-10), 5.64 (dd, 1H, J7,8a = 1.7, J7,8b = 3.9 Hz, H-7),
0
0
5.61 (dd, 1H, H-20), 4.96 (ddd, 1H, J5 ,6 a = 2.5, J5 ,6 b = 3.6 Hz, H-50),
(m, 4 H, arom. H), 5.38 (d, 1H, J1 ,2 = 1.9 Hz, H-10), 5.25 (dd, 1H,
J7,8a = 1.7, J7,8b = 4.5 Hz, H-7), 4.26 (d, 1H, J10,8a = ꢁ1.3 Hz, H-10),
0
0
0
0
0
0
4.83 (dd, 1H, J6 a,6 b = ꢁ12.2 Hz, H-60a), 4.58 (dd, 1H, H-60b), 4.48
(d, 1H, J10,8a = ꢁ1.1 Hz, H-10), 3.74 (s, 3 H, 10-COOCH3), 2.53
(ddd, 1H, J8a,8b = ꢁ15.4 Hz, H-8a), 2.20 (dd, 1H, H-8b), 1.86 (dq,
1H, J13a,14 = 7.3, J13a,13b = ꢁ13.9 Hz, H-13a), 1.57 (dq, 1H,
J13b,14 = 7.3 Hz, H-13b), 1.21 (dd, 1H, H-14).
0
0
3.95 (dd, 1H, J2 ,3 = 3.3 Hz, H-20), 3.88 (dq, 1H, J5 ,6 = 6.2, J5 ,4
=
0
0
0
0
0
0
9.5 Hz, H-50), 3.73 (s, 3 H, 10-COOCH3), 3.55 (dd, 1H, J3 ,4 = 9.5 Hz,
H-30), 3.48 (dd, 1H, H-40), 2.40 (ddd, 1H, J8a,8b = ꢁ15.0 Hz, H-8a),
2.16 (dd, 1H, H-8b), 1.84 (dq, 1H, J13a,14 = 7.3, J13a,13b = ꢁ14.0 Hz,
H-13a), 1.50 (dq, 1H, J13b,14 = 7.3 Hz, H-13b), 1.38 (d, 1H, H-60),
1.15 (dd, 1H, H-14).
0
0
13C NMR (150.90 MHz, CDCl3): d 187.1 (C-5), 187.0 (C-12), 171.7
(10-COOCH3), 166.4 (60-OCOPh), 165.7 (20-OCOPh), 165.6 (40-
OCOPh, 30-OCOPh), 157.0 (C-6), 156.3 (C-11), 136.4–129.1 (arom.
C), 112.5 (C-11a), 111.9 (C-5a), 95.1 (C-10), 71.1 (C-20), 71.0 (C-9),
70.2 (C-50), 70.0 (C-30), 67.7 (C-7), 66.6 (C-40), 62.9 (C-60), 52.6
(10-COOCH3), 52.1 (C-10), 32.7 (C-13), 29.8 (C-8), 6.9 (C-14).
HRMS: calcd for C56H46O17Na1 [M+Na]+ 1013.2633; found
1013.2626.
13C NMR (150.90 MHz, CD3OD + CDCl3): d 186.5 (C-5), 186.4 (C-
12), 171.3 (10-COOCH3), 156.2 (C-6), 155.4 (C-11), 134.9–126.6
(arom. C), 111.4 (C-11a), 111.2 (C-5a), 104.1 (C-10), 72.2 (C-40),
71.4 (C-7), 70.8 (C-30), 70.6 (C-9), 70.3 (C-20), 69.3 (C-50), 51.9
(10-COOCH3), 51.4 (C-10), 33.6 (C-8), 32.0 (C-13), 16.7 (C-60), 6.1
(C-14).