Supporting Information for procedure) (1.5 g, 4.86 mmol) in THF
(40 mL) was added dropwise to the mixture at 0 °C, and the
stirring was continued for 30 min. The mixture was then heated
under reflux for 6 h. Water was added to the mixture at 0 °C to
destroy excess NaH, and after concentration of the mixture, the
residue was extracted with CH2Cl2. The organic layer was
washed with water and dried. Removal of solvent gave a syrupy
liquid, which was chromatographed over silica gel (EtOAc:
petroleum ether, 1:5) giving 8 (1.9 g, 60%) as a colorless foam,
(9H), 1.34 (s, 6H), 1.30 (s, 6H). 13C NMR (75 MHz, CDCl3): δ
165.8 (q), 152.8 (q), 139.2 (q), 137.7 (q), 126.3 (CH), 122.4 (CH),
117.9 (CH), 112.8 (q), 111.8 (q), 109.0 (q), 105.7 (CH), 105.3 (CH),
84.5 (CH), 82.7 (CH), 82.5 (CH), 82.1 (CH), 81.3 (CH), 80.7 (CH),
72.5 (CH), 72.2 (CH2), 72.0 (CH2), 67.4 (CH2), 27.2 (CH3), 26.8
(CH3), 26.7 (2 x CH3), 26.3 (CH3), 25.5 (CH3).
12. [R]25 -54.1 (c 1.19, CHCl3). IR (KBr, cm-1): 3403, 1696,
D
1614. MS (MALDI-TOF): m/z 1966 (M), 1989 (M + Na). 1H NMR
(300 MHz, CDCl3): δ 8.36 (s, 2H), 7.55 (s, 4H), 7.10 (s, 2H), 7.07
(s, 3H), 6.06 (d, 2H, J ) 3.1 Hz), 6.01 (d, 1H, J ) 3.6 Hz), 5.89
(d, 4H, J ) 3.5 Hz), 5.01 (d, 1H, J ) 4.3 Hz), 4.81 (d, 2H, J )
3.0 Hz), 4.66 (s, 8H), 4.60-4.59 (m, 6H), 4.55-4.45 (m, 4H),
4.44-4.23 (m, 10H), 4.14-4.07 (m, 8H), 4.03-3.98 (m, 8H), 1.48
(21H), 1.42 (12H), 1.36 (12H), 1.35 (s, 9H), 1.30 (s,12H). 13C NMR
(75 MHz, CDCl3): δ 166.0 (q), 165.8 (q), 152.8 (q), 139.1 (q), 137.8
(q), 137.5 (q), 126.2 (CH), 122.3 (CH), 117.9 (CH), 113.0 (q), 112.7
(q), 111.7 (q), 109.0 (q), 105.6 (CH), 105.2 (CH), 84.4 (CH), 82.6
(CH), 82.5 (CH), 82.4 (CH), 82.2 (CH), 82.0 (CH), 81.25 (CH),
81.19 (CH), 80.6 (CH), 77.2 (CH), 72.4 (CH), 72.3 (CH2), 72.1
(CH2), 71.9 (CH2), 67.3 (CH2), 27.2 (CH3), 27.0 (CH3), 26.8 (2 x
CH3), 26.4 (CH3), 26.2 (CH3), 25.9 (CH3), 25.4 (CH3). Anal. Calcd
for C97 H132 N2 O40: C, 59.26; H, 6.77; N, 1.42. Found: C, 59.54;
H, 6.97; N, 1.71.
[R]25 -63.8 (c 0.22, CHCl3). IR (KBr, cm -1): 1537. MS (FAB):
D
1
m/z 690 (M + Na). H NMR (300 MHz, CDCl3): δ 8.19 (s, 2H),
7.60 (s, 1H), 5.92 (d, 2H, J ) 3.6 Hz), 4.80 (d, 2H, J ) 12.6 Hz),
4.73 (d, 2H, J ) 12.6 Hz), 4.62 (d, 2H, J ) 3.7 Hz), 4.36 (dt, 2H,
J ) 8.4, 5.7 Hz), 4.16-4.01 (m, 8H), 1.50 (s, 6H), 1.43 (s, 6H),
1.38 (s, 6H), 1.33 (s, 6H). 13C NMR (75 MHz, CDCl3): δ 148.7
(q), 140.0 (q), 131.6 (CH), 121.5 (CH), 111.9 (q), 109.3 (q), 105.3
(CH), 82.6 (CH), 82.2 (CH), 81.3 (CH), 72.3 (CH), 70.9 (CH2),
67.6 (CH2), 26.8 (CH3), 26.7 (CH3), 26.2 (CH3), 25.3 (CH3). Anal.
Calcd for C32H45NO14: C, 57.56; H, 6.79; N, 2.10. Found: C,
57.90; H, 6.51; N, 2.42.
Am in e 9. Aqueous NH4OH (30%, 31 mL) was added dropwise
with stirring to a solution of FeSO4 (22.4 g) in water (84 mL).
After the addition was over, a solution of 8 (1.8 g, 2.7 mmol) in
EtOH (5 mL) was slowly added to the previous mixture of ferrous
hydroxide formed, and the mixture was heated under reflux for
4 h in an atmosphere of N2. After it was cooled to 25 °C, the
mixture was diluted with CH2Cl2 (50 mL) and filtered. The
residue was washed repeatedly with CH2Cl2, and the filtrate was
placed in a separatory funnel. The organic layer was separated,
and the aqueous layer was washed with CH2Cl2 (2 × 30 mL).
The combined organic layer was washed with water and dried.
Removal of solvent afforded a syrupy residue, which on chro-
matography over silica gel (100-200 mesh size; EtOAc:petro-
Meth od B. A solution of 5 (0.2 g, 0.275 mmol), HOBT (0.23
g, 1.70 mmol), and DCC (0.21 g, 1.0 mmol) in CH2Cl2 (5 mL)
was stirred at 0 °C for 1 h and then the mixture was stirred for
another 1 h at 25 °C. It was then cooled to 0 °C and 9 (0.53 g,
0.832 mmol) was added to the mixture and stirred at 25 °C for
72 h. The mixture was then filtered and washed with CH2Cl2.
The organic layer was washed with water, dried and removal of
solvent gave a syrupy liquid, which was chromatographed over
basic alumina (EtOAc:petroleum ether, 1:2) affording 10 (0.46
g, 65%) as a foam.
Hyd r oxy Com p ou n d 13. A solution of 10 (70 mg, 0.027
mmol) in 75% aq. AcOH (5 mL) was stirred for 12 h at 25 °C.
The mixture was then concentrated and the residue was
coevaporated with toluene yielding the diol 13 (60 mg, 95%) as
a white foam, IR (KBr, cm-1): 3397, 1677, 1614. MS (MALDI-
TOF): m/z 2346 (M + H). 1H NMR (300 MHz, CDCl3): δ 8.59
(s, 3H), 7.38 (s, 6H), 7.09 (s, 3H), 6.82 (s, 3H), 6.08 (d, 3H, J )
3.3 Hz), 5.91 (d, 6H, J ) 3.3 Hz), 4.81 (d, 3H, J ) 2.7 Hz), 4.66-
4.57 (m, 18H), 4.49-4.45 (m, 6H), 4.24-4.21 (m, 6H), 4.03 (m,
18H), 3.79-3.76 (m, 6H), 3.58-3.56 (m, 6H), 1.53 (s, 9H), 1.48
(s, 18H), 1.38 (s, 9H), 1.32 (s, 18H). 13C NMR (75 MHz, CDCl3):
δ 166.7 (q), 138.9 (q), 137.5 (q), 137.0 (q), 124.7 (CH), 123.0 (CH),
118.8 (CH), 113.0 (q), 111.7 (q), 105.7 (CH), 105.0 (CH), 82.3
(CH), 82.0 (CH), 81.9 (CH), 81.8 (CH), 81.3 (CH), 80.0 (CH), 71.9
(CH2), 71.3 (CH2), 68.8 (CH), 64.7 (CH2), 27.0 (CH3), 26.6 (CH3),
26.5 (CH3), 26.2 (CH3). Anal. Calcd for C111H153N3O51: C, 56.84;
H, 6.58; N, 1.79. Found: C, 56.56; H, 6.84; N, 2.07.
leum ether, 1:4) gave 9 (1.48 g, 86%) as a pale yellow foam, [R]25
D
-31.7 (c 2.54, CHCl3). IR (KBr, cm -1): 3462, 3372, 1610; MS
(FAB): m/z 638 (M + H), 660 (M + Na). 1H NMR (300 MHz,
CDCl3): δ 6.64 (s, 1H), 6.62 (s, 2H), 5.89 (d, 2H, J ) 3.7 Hz),
4.61-4.57 (m, 6H), 4.38-4.32 (m, 2H), 4.15-4.00 (m, 8H), 1.49
(s, 6H), 1.43 (s, 6H), 1.38 (s, 6H), 1.31 (s, 6H). 13C NMR (75 MHz,
CDCl3): δ 146.8 (q), 139.2 (q), 116.7 (CH), 113.5 (CH), 111.8 (q),
109.0 (q), 105.3 (CH), 82.7 (CH), 81.7 (CH), 81.3 (CH), 72.5 (CH),
72.2 (CH2), 67.4 (CH2), 26.9 (CH3), 26.8 (CH3), 26.3 (CH3), 25.5
(CH3). Anal. Calcd for C32H47NO12: C, 60.27; H, 7.43; N, 2.20.
Found: C, 60.26; H, 7.12; N, 2.46.
Den d r itic Com p ou n d 10: Meth od A. To a solution of 5 (0.2
g, 0.275 mmol) and 9 (0.53 g, 0.832 mmol) in CH2Cl2 (2.5 mL),
DCC (0.2 g, 0.970 mmol) was added at 0 °C with stirring, and
the stirring was continued at 25 °C for 48 h. The mixture was
then filtered and washed with CH2Cl2. The organic layer was
washed with water, dried, and removal of solvent gave a syrupy
liquid, which was chromatographed over basic alumina (EtOAc:
petroleum ether, 1:2) affording 10 (0.142 g, 20%). Further elution
afforded 12 (0.216 g, 40%) and 11 (0.056 g, 15%). 10: [R]25D -66.1
(c 1.09, CHCl3). IR (KBr, cm-1): 1693, 1610. MS (MALDI-
TOF): m/z 2585.6 (M + H). 1H NMR (600 MHz, CD3OD): δ 7.60
(s, 6H), 7.13 (s, 3H), 6.83 (s, 3H), 6.09 (d, 3H, J ) 3.5 Hz), 5.88
(d, 6H, J ) 3.7 Hz), 4.77 (d, 3H, J ) 3.5 Hz), 4.68 (d, 6H, J )
11.8 Hz), 4.67 (m, 6H), 4.61 (m, 3H), 4.59 (d, 6H, J ) 11.8 Hz),
4.34 (ddd, 6H, J ) 7.3, 6.3, 5.5 Hz), 4.14 (m, 3H), 4.12 (m, 6H),
4.12 (d, 3H, J ) 12.4 Hz), 4.06 (d, 3H, J ) 12.4 Hz), 4.02 (dd,
6H, J ) 8.5, 5.5 Hz), 3.98 (d, 6H, J ) 3.2 Hz), 3.91 (dd, 6H, J )
8.5, 5.5 Hz), 1.52 (s, 9H), 1.45 (s, 18H), 1.41 (s, 9H), 1.38 (s, 18H),
1.31(s, 18H), 1.27 (s, 18H). 13C NMR (75 MHz, CDCl3): δ 165.8
(q), 139.1 (q), 137.7 (q), 137.5 (q), 126.0 (CH), 122.3 (CH), 118.0
(CH), 112.9 (q), 111.8 (q), 109.0 (q), 105.6 (CH), 105.2 (CH), 82.6
(CH), 82.3 (CH), 82.0 (CH), 81.2 (CH), 77.2 (CH), 72.4 (CH), 72.1
(CH2), 71.9 (CH2), 67.3 (CH2), 27.0 (CH3), 26.8 (2 x CH3), 26.5
(CH3), 26.2 (CH3), 25.4 (CH3). Anal. Calcd for C129H177N3O51: C,
59.92; H, 6.90; N, 1.63. Found: C, 59.63; H, 6.63; N, 1.54.
11. MS (MALDI-TOF): m/z 1345.4 (M + H). 1H NMR (300
MHz, CDCl3): δ 8.34 (s, 1H), 7.56 (s, 2H), 7.13-7.11 (m, 4H),
6.08-6.04 (m, 3H), 5.89 (d, 2H, J ) 3.6 Hz), 5.03 (br, 2H), 4.82
(d, 1H, J ) 3.1 Hz), 4.47-4.46 (m, 12H), 4.40-4.28 (m, 4H),
4.15-3.99 (m, 12H), 1.49 (s, 9H), 1.47 (s, 6H), 1.42 (s, 6H), 1.37
Ack n ow led gm en t. Thanks are due to CSIR, India,
for the award of a J unior Research Fellowship to S. G..
Sincere thanks are extended to Dr. Michel Chre´tien for
his interest in this work. A. Basak is thankful to the
Canadian Foundation of Innovation (CFI), the Ontario
Research and Development Fund (ORDF), and the
University of Ottawa for financial support. A.M. thanks
the National Science Foundation (USE-9052233) and
the departments of chemistry and biochemistry and the
graduate program in biotechnology at Manhattan Col-
lege for funding. We thank Dr. V. S. Giri, Dr. R.
Mukhopadhyay, Mr. A. K. Banerjee, and Mr. K. Sarkar
for NMR and mass spectral analyses, and Mr. S.
Choudhury for general assistance.
Su p p or tin g In for m a tion Ava ila ble: Preparative proce-
1
13
dure for 7. H and C NMR spectra of 3-5 and 7-13. This
material is available free of charge via the Internet at
http://pubs.acs.org.
J O0264168
620 J . Org. Chem., Vol. 68, No. 2, 2003